Blends and alloys of polycyclic polymers

ABSTRACT

Polycyclic addition polymers derived from norbornene-type monomers are mixed with a variety of other polymers to generate families of new blends, alloys, and block copolymers.

BACKGROUND OF THE INVENTION

Addition polymers derived from norbornene-type monomers exhibit a numberof physical and mechanical properties, some of which are highlydesirable while others are less desirable or even undesirable. Forexample, the addition homopolymer of norbornene, i.e.,poly(bicyclo[2.2.1.]hept-2-ene) exhibits some excellent characteristicssuch as optical clarity, low moisture absorption, and extremely highthermomechanical resistance having a glass transition temperature ofabout 380° C. On the other hand, this same homopolymer is very brittlerequiring improved toughness for many applications. A well knowneffective method of improving the properties of a polymer is to blend oralloy the polymer with another polymer (or polymers) in order tooptimize a given property, e.g., toughness or heat distortiontemperature.

A polymer blend is simply a mixture of two or more polymers. The polymerblend, however, can be either immiscible or miscible depending on thevalue of the free energy of mixing between the polymeric species. For anegative free energy of mixing, the thermodynamics are favorable for amiscible polymer blend; typically a one-phase system results. For apositive free energy of mixing an immiscible polymer blend resultsgiving, typically, a multi-phase system. To change the morphology of ablend, the interfacial properties of the blend must be changed. Onemethod to accomplish this is to add a compatibilizing agent to theblend. According to L. A. Utracki (Polymer Alloys and Blends.Thermodynamics and Rheology. Hanser, Munich, 1989, p. 124) the “goal ofcompatibilization is to obtain a stable and reproducible dispersionwhich would lead to the desired morphology and properties.” This can beaccomplished in the following ways: 1) add linear, graft, or randomcopolymers to a polymer blend; 2) coreact in the blend to generatein-situ either copolymer, interacting polymers or interpenetratingnetworks (by the synthesis of one of the polymers in the presence of thesecond polymeric constituent); or 3) modify the homopolymers byincorporation of functional groups. In many cases this may result in theformation of a polymer alloy, that is, an immiscible polymer blendhaving a modified interface or morphology. The morphology of the polymeralloy may be a very fine (sub-micron) dispersion or relatively largedepending on the compatibilizer chosen, the amount of compatibilizeradded, and the desired properties of the alloy.

Incompatibility is the rule rather than the exception, particularly inthe case of hydrocarbon addition polymers derived from norbornene-typemonomers (e.g., polynorbornene). Blends of incompatible polymers in mostinstances form large domains with properties inferior to theconstituents, therefore compatibilizer techniques are usually employedto maximize the strengths of the constituents while overcoming theirindividual deficiencies. Various attempts have been undertaken toprepare polymer compositions that are easily processable and whichpossess improved physical properties. Compatibilization can provide forspecific interactions between polymers. In this regard, methods havefocused upon the preparation and use of functionalized polymers havingpendant reactive groups which facilitate the grafting of coreactivematerials and other polymers to form graft-modified polymers and polymerblends having improved physical properties. Typically a polymer can befunctionalized by copolymerizing the monomer with monomer(s) having afunctional substituent. However, polyolefins particularlypolynorbornene-type addition polymers are generally more difficult tofunctionalize by copolymerization processes because of the tendency ofthe polar groups in the monomers to poison the catalyst. To ourknowledge no attempts have been made to prepare blends and alloys ofpolycyclic addition polymers derived from norbornene-type monomers witha variety of other dissimilar polymers.

Accordingly, it would be highly desirable to provide blends and alloysof addition polymerized norbornene-type monomers with other polymersystems.

SUMMARY OF THE INVENTION

We have found that it is possible to functionalize polynorbornene-typepolymers so as to make them compatible and hence alloyable with avariety of other polymers to generate families of new blends, alloys,and block copolymers with superior balance of properties.

It is a general object of this invention to provide a functionalizedpolycyclic addition polymer derived from NB-type monomers.

It is another object of this invention to provide polycyclic additionpolymers containing a terminal functional group.

It is a further object of this invention to provide polycyclic additionpolymers that contains pendant functional groups.

It is still a further object of the invention to provide free radicalgraft copolymers of polycyclic addition polymers having pendantpolyvinylic side blocks and maleic anhydride grafts.

It is another object of this invention to provide in situ polymerizationblends of polycyclic addition polymers and reactive and nonreactiveelastomeric polymers.

It is still a further object of the invention to provide chlorinatedpolycyclic addition polymers.

It is another object of the invention to provide miscible blends ofpolycyclic addition polymers and polystyrene.

In still another object of the invention to provide methods that enablefunctional end groups and functional pendant groups to be tailored sothat desired reactions can be effected.

It is still another object of the invention to prepare olefinic A-Bblock copolymers with pendant polynorbornene-type side blocks.

It is a further object to react the terminal functional polycyclicaddition polymers of this invention with coreactive monofunctional anddifunctional polymeric materials to make A-B and A-B-A block copolymers.

We have found that it is possible to functionalize polycyclic additionpolymers derived from NB-type monomers to make new materials that can beutilized as: 1) intermediates for the preparation of other functionalcontaining polymers; 2) segment polymers for the preparation of blockcopolymers; 3) substrate polymers for the preparation of graftcopolymers; 4) as constituent polymers in the preparation of in situpolymer blends; 5) polymers in miscible blends; 6) compatibilizers forpolymer blends; and 7) thermosetting systems.

These and other objects of the present invention are accomplished by thefollowing methods and functionalized PNB compositions. As usedthroughout the specification, the term PNB means polymers represented bystructure II below.

DETAILED DESCRIPTION

The polycyclic addition polymers of this invention are derived from atleast one norbornene-type (NB-type) monomer having the followingstructure:

wherein R¹ to R⁴ independently represent hydrogen, linear and branched(C₁-C₂₀) alkyl; hydrocarbyl substituted and unsubstituted (C₅-C₁₂)cycloalkyl; substituted and branched (C₅-C₁₋) cycloalkenyl (C₆-C₂₄)aryl; (C₇-C₁₅) arakyl; linear and branched (C₂-C₂₀) alkenyl; (C₃-C₂₀)alkynyl; any of R¹ and R² or R³ and R⁴ can be taken together to form a(C₁-C₁₀) alkylidene group; R¹ and R⁴ when taken together with the tworing carbon atoms to which they are attached can represent saturated andunsaturated cyclic groups of 4 to 12 carbon atoms or any aromatic ringof 6 to 17 carbon atoms; and n is 0, 1, 2, 3, or 4. When n is 0 instructures I and II and in all structures in the specification andclaims, it will be recognized that a bicyclic structure will be presentand that substituents R¹ to R⁴ will be attached to the respective ringcarbon atoms in the bicyclic ring. By hydrocarbyl is meant that thesubstituent is composed solely of carbon and hydrogen atoms.Representative hydrocarbyl substituents include linear and branched(C₁-C₁₀) alkyl, and linear and branched (C₂-C₁₅) alkenyl.

The term NB-type monomer as used throughout the present specification ismeant to include norbornene as well as any higher cyclic derivativethereof so long as the monomer contains at least one norbornene moietyas set forth in the structure above.

Representative monomers of structure I include 2-norbornene,5-methyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene,5-phenyl-2-norbornene, 5-naphthyl-2-norbornene,5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-hexenyl-2-norbornenedicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene,methyltetracyclododecene, tetracyclododecadiene,dimethyltetracyclododecene, ethyltetracyclododecene, ethylidenyltetracyclododecene, phenyltetracyclododecene, trimers of cyclopentadiene(e.g., symmetrical and asymmetrical trimers).

The polycyclic polymers (NB-type polymers or PNB's) derived from themonomers described under structure I above are represented by thefollowing structure:

wherein R¹ to R⁴ and n are defined above; and a represents the number ofrepeating units present in the polymer. This invention contemplateshomopolymers and copolymers containing the repeat unit describedgenerally under structure II. The structural repeat units derived fromthe NB-type monomers of this invention insert into the polymer backbonevia linkages derived from the double bond present in the norbornenemoiety (i.e., 2,3-enchainment). The repeating units are joined directlyto one another without any intermediate linkages between units. Thepolymer backbone is free of olefinic unsaturation.

In the first embodiment of this invention functionalized PNB's can beprepared from PNB's containing terminal olefinic unsaturation. Byterminal olefinic is meant that the PNB is terminated with an α-olefin,isobutylene, or diisobutylene as follows.

wherein R⁵ is hydrogen or linear or branched (C₁-C₁₀) alkyl.Representative R⁵ substituents include hydrogen, methyl, ethyl, propyl,i-propyl, butyl, t-butyl, and pentyl radicals. Terminal olefinicunsaturation and terminal isobutylene, or diisobutylenepolynorbornene-type polymers containing unsaturation can be prepared bythe novel chain transfer mechanism of the catalyst system of copendingpatent application U.S. Ser. No. 08/339,863 filed on Nov. 15, 1994,which is incorporated herein by reference. Terminal unsaturated PNB'ssuch as vinyl-terminated and isobutylene-terminated PNB, provide anentry point to access a host of functionalized PNB's specifically at thepolymer chain end. These polymer chain end functional PNB's can beaccessed by a variety of stoichiometric as well as catalytic reactionsknown to those skilled in the art of carbon-carbon double bondchemistry.

PNB's having terminal olefinic moieties can be functionalized byformation of, but are not limited to, epoxy, monoalcohol, diol,anhydride, aldehyde, carboxylate, dicarboxylate, amide, nitrile, amine,and sulfonate moieties.

Terminal PNB-epoxides can be prepared from the reaction of an α-olefinor isobutylene terminated PNB and m-chloro-perbenzoic acid (MCPBA) in anappropriate solvent as follows:

The terminal PNB-epoxides can also be prepared by reaction with otherhydroperoxide or hydroperoxide mixtures such as t-butylperoxide orhydrogen peroxide and acetic acid mixtures as related by J. H. Bradburyand M. C. Seneka Perera in Ind. Eng. Chem. Res. 1988, 27, 2196. ThePNB-epoxides can also be prepared via catalytic epoxidations usingwell-known transition metal catalysts as detailed by K. B. Sharpless andT. R. Verhoeven in Aldrichimica Acta 1979, 12, 63.

The terminal PNB-monoalcohol can be prepared from the reaction of vinylterminated PNB with 9-borobicyclo[3.3.1]nonane (9-BBN) followed byhydrogen peroxide, and NaOH in an appropriate solvent as follows:

The terminal anhydride-PNB can be prepared by the reaction ofisobutylene terminated PNB and maleic anhydride (ene reaction). Thereaction is schematically represented as follows:

The terminal anhydride-PNB can be further reacted under acidic or basicconditions to form a dicarboxylate functional-PNB.

The diol terminated PNB can be prepared by the reaction of an epoxyterminated PNB with HClO₄/H₂O (perchloric acid). The reaction scheme isset forth below:

The aldehyde terminated PNB can be prepared from the hydroformylation ofan isobutylene terminated PNB as shown below:

It is also contemplated that the aldehyde end group moiety can befurther reacted with hydrogen to form the alcohol-terminated PNBcatalytically. This transformation is well-known to those skilled in theart of the “oxo” process as described in Principles and Applications ofOrganotransition Metal Chemistry by J. P. Collman, L. S. Hegedus, J. R.Norton, and R. G. Finke, University Science Books, Mill Valley, Calif.,2nd ed., 1987, p. 621 and in Homogeneous Catalysis by G. W. Parshall andS. D. Ittel, John Wiley & Sons, 2nd ed., 1992, p. 106. Thistransformation is typically carried out using a suitable cobalt orrhodium catalyst such as phosphine-modified dicobalt octacarbonyl andphosphine-modified rhodium complexes.

Further catalytic transformations of the terminal olefinic unsaturatedPNB are contemplated such as, but not limited to, azacarbonylation,hydrocarboxylation and hydrocyanation to yield amide-functional,carboxylate or carboxylic acid-functional, and nitrile-functional PNB's,respectively. Azacarbonylation is typically carried in the presence ofmainly nickel and cobalt catalysts and in presence of ammonia, aliphaticamines, or aromatic amines as related by I. Tkatchenko in Comp.Organomet. Chem. G. Wilkinson, F. G. A. Stone, E. W. Abel, eds.,Pergamon, 1982, vol. 8, p. 173. Hydrocarboxylation is typically carriedout in the presence of a cobalt catalyst such as dicobalt octacarbonylunder CO pressure in either an alcohol (to form the carboxylate) orwater (to form the carboxylic acid) cosolvent as related in HomogeneousCatalysis by G. W. Parshall and S. D. Ittel, John Wiley & Sons, 2nd ed.,1992, p. 101. Hydrocyanation is typically carried out in the presence ofnickel tetrakis(phosphine) or phosphite complexes and hydrogen cyanideas related in Homogeneous Catalysis by G. W. Parshall and S. D. Ittel,John Wiley & Sons, 2nd ed., 1992, p. 42. It is further contemplated thatthe nitrile functionality can be hydrogenated to the terminal aminefunctionality using stoichiometric reagents such as lithium aluminumhydride or catalysts such as RhH(PPr^(i) ₃)₃ and H₂ or Raney nickel andsodium borohydride in alcohols.

A further embodiment of this invention includes the sulfonation of theterminal olefinic unsaturated PNB using sulfonation reagents such asacetyl sulfate (a mixture of sulfuric acid and acetic anhydride). Thistransforms the terminal olefinic unsaturated PNB into a sulfonic acidthat may be neutralized using bases such as lithium hydroxide ormagnesium hydroxide to form ionomeric species.

The acrylate terminated PNB can be prepared by the reaction of ahydroxy-terminated PNB and acryloyl chloride as shown by the followingreaction scheme:

The terminal olefinic, isobutyl, and diisobutyl PNB polymers used in thepreparation of terminal functional PNB's of this invention can beprepared from a reaction mixture comprising one or more norbornene-typemonomer(s), a [(crotyl) Ni(COD)][LPF₆] catalyst in the presence of achain transfer agent (CTA) all in an appropriate solvent. The CTA isselected from a compound having a terminal olefinic double bond betweenadjacent carbon atoms, wherein at least one of the adjacent carbon atomshas two hydrogen atoms attached thereto. The CTA is represented by theformulae:

wherein R⁵ is as defined above. Preferred CTA's include ethylene,propylene, isobutylene, 4-methyl-1-pentene, 1-hexene, 1-decene, and1-dodecene.

The CTA's incorporate exclusively as terminal end-groups on each PNBchain. The CTA's do not copolymerize into the PNB backbone. Arepresentative structure is shown below:

wherein Q is derived from the CTA defined above.

The terminal functional PNB polymers of this invention can be reactedwith any coreactive moiety containing a functional group that isreactive with the terminal functional group on the PNB polymer. Thecoreactive moiety can be monomeric, oligomeric, or polymeric and theterm as used herein refers to coreactive plasticizers, lubricants,impact modifiers, heat distortion modifiers, processing aids,compatibilizers, and polymers.

The terminal functional PNB's of this invention can be utilized toprepare A-B and A-B-A block copolymers of PNB with coreactive polymer,oligomers or macromonomers having a functional group (preferablyterminal functional) that is reactive with the terminal functional groupon the PNB.

Exemplary of the block copolymers that can be prepared in accordancewith this invention is the reaction of a monohydroxy terminated PNB witha monofunctional moiety (e.g., acid chloride) to give an A-B blockcopolymer as follows:

wherein R⁶ polybutadiene, polyisoprene, polystyrenepoly(α-methylstyrene), polymethylmethacrylate, polyalkylacrylates suchas polybutylacrylate, or other anionically polymerized polymers that canbe functionalized to an acid.

If a difunctional acid chloride is employed, an A-B-A block copolymercan be obtained as follows:

wherein R⁷ represents polybutadiene, polyisoprene, polystyrene,poly(α-methylstyrene), polybutylacrylate, polyester, polyamide, polyamicester, polyether.

If a monofunctional isocyanate is employed, the PNB will be end-cappedwith an urethane group as follows:

wherein R⁸ is hydrocarbyl and silyl such as (trialkoxy)silyl isocyanate.By hydrocarbyl is meant linear and branched (C₁-C₁₅) alkyl, linear andbranched (C₁-C₂) alkenyl, (C₆-C₂₀) aryl, and aralkyl (C₆-C₁₅).

The case of a diisocyanate the following A-B-A block copolymer isformed:

wherein R⁹ represents a polyurethanes, polyureas, and polythioureas.

Vinyl terminated PNB can be subjected to a hydrosilation reaction in thepresence of a platinum catalyst as related by J. L. Speier in Advancesin Organometallic Chemistry 1979, Vol. 17, p. 407, to give A-B-A blockcopolymers wherein the PNB comprises the A blocks with a polysiloxane Bblock as follows:

wherein R¹⁰ independently represents (C₁-C₁₅) alkyl, (C₆-C₂₀) alkyl, or(C₆-C₂₄) aralkyl, m is 2 to 10, a represents the number of repeatingunits of the siloxane unit.

In this same manner epoxy terminated PNB can be reacted with adifunctional acid terminated polybutadiene (HOOC-polybutadiene-COOH) oran aliphatic diacid (HOOC-R-COOH) to give A-B-A block copolymerproducts.

In addition, polymers with terminal-olefin unsaturation such as, forexample, allyl terminated polyisobutylene can be directly appended tothe terminal end of a PNB via the chain transfer mechanism utilized toprepare the olefin terminated PNB starting materials of this embodiment.In this manner a variety of PNB A-B block copolymers can be synthesized.Other polymers that can function as polymeric chain transfer agents areolefinic terminated polyolefins such as polyethylene, polypropylene, andethylene/propylene (diene) rubber.

In another embodiment of this invention functionalized PNB's can beprepared from PNB starting materials that contain olefinic unsaturationthat is pendant from the polycyclic structural repeat unit (i.e.,pendant olefinic PNB). Groups that provide pendant olefinic unsaturationare (C₁-C₁₀) alkylidene (C₂-C₁₀) alkenyl wherein the unsaturated doublebond is at the terminal end of the substituent (C₅-C8) cycloalkenyl, anda (C5-C₈) fused ring cycloalkenyl ring structure. Preferred substituentsinclude ethylidene, vinyl, cyclohexenyl, and a cyclopentene ring takentogether with two adjacent carbon atoms on the polycyclic repeating unit(i.e., dicyclopentadiene). Representative PNB's with pendantunsaturation are set forth as follows:

where a represents the number of repeating units in the polymer. Itshould be understood that the PNB's so functionalized can include repeatunits set forth under formula I.

The foregoing polymers are polymerized from one or more of monomersselected from formula I. Homopolymers and copolymers are contemplatedwithin the scope of this embodiment.

The PNB's with pendant unsaturation are made by copolymerization of therespective comonomer constituents using nickel-based catalysts. Thenickel-based catalyst system may include the addition of nickel-(II)ethylhexanoate to a dichloroethane solution of the comonomers and asuitable chain-transfer agent (an alpha-olefin such as 1-decene) ifdesired to control molecular weight, followed by the addition of atrialkyl aluminum (e.g., triethylaluminum, tri-iso butylaluminum, etc.),followed by a chlorinated activator (e.g., hexachloroacetone, chloranil,etc.). Additionally the nickel-based catalyst system may include theaddition of a Brønsted acid such as HSbF₆ to nickel (II) ethylhexanoate,followed by addition of this mixture to a dichloroethane solution of thecomonomers (optionally including a chain-transfer agent), followed byaddition of BF₃.Et₂O and a trialkylaluminum such as triethylaluminum.

As with the PNB's containing terminal olefinic unsaturation, the PNB'scontaining pendant unsaturation can be functionalized to form epoxy,monoalcohol, diol, carboxylate, anhydride, sulfonate, amide, nitrile,and amine. The PNB's containing pendant olefinic groups can be preparedin the same manner as described above for the PNB's containing terminalolefinic groups. The following reaction scheme is illustrative ofpendant olefinic PNB functionalization via epoxidation.

The pendant epoxide functionality can be converted to the diol asdescribed above in the terminal functional epoxide embodiment. As withthe terminal functional epoxy PNB's, the PNB's with pendant epoxidefunctionality can be coreacted with acid and diacid chlorides set forthabove to give A-B and A-B-A block copolymers. In general the epoxidependant functionality undergoes any reaction that the monoepoxidesdiscussed above can undergo.

Polynorbornene copolymers such as PNB/ENB, PNB/vinyl norbornene,PNB/cyclohexyl norbornene and PNB/DCPD, most preferably PNB/DCPDcopolymer containing reactive unsaturated groups and whose molecularweight (M_(n)) ranges from 225 to 15,000 g/mole, preferably range beingfrom 1,000 to 5,000 g/mole, can be epoxidized using peracids such asperacetic acid, perbenzoic acid, m-chloro perbenzoic acid, mostpreferably m-chloro perbenzoic acid. Such epoxidized PNB copolymers canbe used as multifunctional epoxy material in standard epoxy formulationsto obtain a three dimensional insoluble and infusible network. Thusepoxidized PNB copolymers can be dissolved in both aromatic andaliphatic di and multifunctional epoxy resins such as Epon 828, epoxyphenolic novolac resins, epoxy cresol novolac resins,3′,4′,epoxycyclohexylmethyl 3,4-epoxy cyclohexanecarbonate, 3,4-epoxycyclohexyloxirane, 2-(3′,4′-epoxycyclohexyl)-5,1′-spiro-3′,4′-epoxycyclohexane-1,3-dioxane, the most preferred being the 3,4-epoxycyclohexyloxirane, and treated with a hardener or curing agent; itschoice depending on the processing method, curing condition and theproperties desired. The hardener can be either catalytic or coreactivein nature. Catalytic curing agent could be trialkyl amines, borontrifluoride amine complexes and photoinitiated cationic curing agentssuch as aryldiazonium salts, diaryliodonium salts and onium salts ofgroup VI a elements, especially salts of positively charged sulfurcompounds. The most preferred catalytic hardener is the borontrifluoride amine complexes. Coreactive hardeners can be selected fromprimary and secondary aliphatic and aromatic amines, such as methylenediamine, diaminodiphenyl sulfone, dicynadiamide, diethylenetriamine,triethylenetetramine, preferably diaminodiphenyl sulfone, aliphatic andaromatic mercaptans, di and multifunctional isocyanate, di andmultifunctional polyester and polyether carboxylic acids and acidanhydrides. Selected acid anhydrides are phthalic anhydride,tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride,hexahydrophthalic anhydride, nadic methyl anhydride and chlorendicanhydride. Thus the epoxy resin containing 10 to 50 weight percent ofepoxidized PNB copolymer, the most preferable amount being from 5 to 25wt. %, can be treated with the hardener at temperatures ranging fromabout 80° C. to about 200° C. depending on the hardener of choice andthe properties of the network desired. The most preferred temperaturebeing 150° C. These PNB copolymer containing materials are phaseseparated in nature with the domain size of the PNB phase depending onthe molecular weight and the functionality of the epoxidized PNBcopolymer used. The multifunctional epoxy materials of this inventionprovide crosslinked materials with high glass transition temperature,low moisture uptake, good electrical properties, good corrosion/solventresistance and low shrinkage on cure.

Thermosets can also be prepared from the PNB's having pendantunsaturation by heating the homopolymers or copolymers containingpendant vinyl, alkylidene such as ethylidene, fused ring cyclopentenyl,cyclopentenyl and cyclohexeneyl in the presence of a free radicalpolymerization initiator such as azobisisobutyonitrile, benzoylperoxide, lauroyl peroxide, t-butylperoxypivalate,t-butylperoxyacetoate, and α-cumyl peroxyneodecaneoate in an approatesolvent. Suitable solvents include hydrocarbons, halohydrocarbons,aromatics and haloaromatics. The amount of peroxide initiator rangesfrom about 0.1 to 5.8% by weight after polymer.

Because of the exceptionally high temperature properties of polycyclicaddition polymers, it would be useful to blend them with polymer systemsof lesser high temperature properties (e.g., heat distortion) in orderto raise the heat distortion properties of the target system. However,in order to make an effective blend it is necessary that the polymercomponents exhibit at least partial miscibility and that some degree ofdomain size control be achievable. For example, it would be highlydesirable to improve the heat distortion temperature of CPVC in order toincrease its commercial applicability in high temperature applications,e.g., high temperature pipe, etc. However, CPVC and polynorbornene(non-functionalized) are completely immiscible and the resulting blendexhibits no useful improvement in properties. We have discovered that byintroducing epoxy functionality into the PNB (e.g., terminal and/orpendant functional) yields optically clear blends with CPVC which isparticularly attractive due to the stabilizing effects of the epoxidemoiety against dehydrohalogenation.

The CPVC polymers suitable for use in the blends of this invention arereadily commercially available. The chlorine content typically rangesfrom about 61 to about 72 weight percent, preferably from about 63 toabout 68 weight percent. The inherent viscosity of the CPVC ranges fromabout 0.46 to about 1.2, preferably from about 0.68 to about 0.92. Theinherent viscosity (I.V.) is a representative measure of the molecularweight of a polymer and is obtained in accordance with ASTM D-1243-66.

In another embodiment of the invention polycyclic polymers derived fromNB-type monomers can be modified by grafting free radical polymerizablemonomers forming grafted side chains to or from the polycyclic backboneof the PNB. In this embodiment free radically polymerizable monomerscontaining vinyl unsaturation, i.e., a H₂C═C (moiety can be polymerizedin the presence of the PNB. The PNB is dissolved in a common solvent forthe PNB and vinyl-type monomer. A free radical catalyst initiator isadded to the medium and the medium is then heated at elevatedtemperature to conduct the grafting reaction.

Suitable solvents include hydrocarbons, halohydrocarbons, aromatics, andhaloaromatics. Preferred solvents are the aromatics and haloaromaticssuch as toluene, xylene, benzene, and chlorobenzene. It should be notedthat the vinyl-type monomer can function as the solvent so long as itcan dissolve the PNB. For example, PNB was observed to be soluble instyrene. In this case an additional solvent is not necessary.

The temperature range of the reaction is from about 80° C. to about 150°C., preferably about 120° C.

Suitable catalytic initiators include organic peroxides such as lauroylperoxide, benzoyl peroxide, diacetyl peroxide,5-butyl-peroxyneodeconate, t-butylcumyl peroxyneodecanoate, di-n-propylperoxydicarbonate, di-t-butyl peroxide, anddi-sec-butyl-peroxydicarbonate. The preferred peroxide is di-t-butylperoxide.

Exemplary of the vinyl-type monomers are styrenes, acrylates,methacrylates, acrylamides, acrylonitriles, and vinyl monomers.

The styrenes are selected from compounds of the formula:

wherein n is independently 0, 1, 2, 3, 4, or 5, R¹⁰ is hydrogen ormethyl, and R¹¹ independently represents, hydrogen, halogen, linear andbranched (C₁-C₆) alkyl, (C₆-C₁₂) alkoxy, (C₆-C₂₀) aryl, (C₆-C₂₀)aryloxy, —N(R¹²)₂, —SO₂R¹², where R¹² independently represents hydrogen,linear, and branched (C₁-C₁₀) alkyl, and (C₆-C₁₂) aryl andtrifluoromethyl. Preferred compounds of the above formula includesstyrene and α-methyl styrene.

The acrylates and methacrylates are selected from compounds of theformula:

wherein R¹² is hydrogen, linear, or branched (C₁-C₅) alkyl, (C₆-C₁₂)alkyl, nitrile, and halogen; R¹³ is hydrogen, linear, or branched(C₁-C₂₀) alkyl, (C₁-C₁₀) hydroxy substituted alkenyl.

The acrylamides are selected from compounds of the formula:

wherein R¹⁵ is hydrogen, linear, or branched (C₁-C₅) alkyl, (C₆-C₁₂)aryl, and halo; R¹⁶ independently represents hydrogen, linear, orbranched (C₁-C₅) alkyl, and (C₆-C₁₂) aryl.

The acrylonitriles are selected from compounds of the formula:

wherein R¹⁷ is hydrogen, linear, or branched (C₁-C₅) alkyl, (C₆-C₁₂)aryl, halo, and nitrile.

The vinyl monomers are selected from compounds of the formula:

wherein R¹⁸ is hydrogen, Cl, Br, and F, linear or branched (C₁-C₅)alkyl, (C₆-C₁₂) aryl; and X is Cl, Br, F, linear or branched (C₁-C₅)alkyl, (C₂-C₂₀) alkenyl, (C₆-C₁₂) aryl, (C₆-C₁₈ aryl ethers, —OAc, arylethers, tri (C₁-C₁₀) alkoxysilanes, and allyl (C₁-C₁₀) trialkoxysilanes.

In a preferred embodiment, is has been discovered that the PNB'scontaining pendant unsaturation on the PNB backbone enhance the graftingof the free radically polymerized side chains on to the PNB backbone. Itis thought that the allylic hydrogen atoms (exclusive of the bridgeheadhydrogens) provides an active site for more efficient grafting of thefree radically polymerized vinyl-type monomer.

Another embodiment of this invention concerns a process and polymercomposition in which an elastomer is solution blended withnorbornene-type monomer(s) in a suitable solvent (i.e., a solvent thatdissolves the norbornene-type monomer, the resulting norbornene-typepolymer, and the elastomer but does not interfere with thepolymerization). The norbornene-type monomer is then polymerized byaddition of a multicomponent catalyst system comprising a Group VIIItransition metal compound in combination with an organoaluminum compoundand an optional third component selected from Lewis acids, Brønstedacids, and halogenated compounds. Such catalysts are described incopending U.S. patent application Ser. No. 08/339,863 filed on Nov. 15,1994 which is herein incorporated by reference. In this one-stepprocess, a more intimate mixture or blend of the elastomer and theresulting polynorbornene is formed than can be obtained by meltblending. This process referred to herein as nonreactive in situblending because no covalent bonding occurs between the subsequentlyformed PNB and elastomer. The same morphology is obtained by solutionblending a completely polymerized PNB and mixing with an elastomer.Likewise, unreacted blends with suitable plasticizers have been found tobe a miscible with NB-type polymers exhibiting a reduced glasstransition for the blend. Suitable plasticizers include hydrogenatedcyclopentadiene oligomers (sold under the trademark Escorez® by ExxonChemicals) and at linear and branched alkane ranging from C₁₄-C₃₄, mostpreferably C₂₄-C₃₀.

In this case an elastomer is defined as any polymeric material which hasa low glass transition temperature (T_(g)). Low glass transitiontemperature is defined as T_(g)'s below room temperature. Examples ofelastomers include butyl rubber, polyisobutylene, and ethylene/propylene(diene) rubber. Other suitable elastomers include polysiloxanes (e.g.,polydimethylsiloxane, etc.) and poly(meth)acrylates (e.g.,polybutylacrylate, polybutylmethacrylate, etc.).

Another class of polymers having elastomeric properties which aresuitable for forming unreactive in situ blends with norbornene-typepolymers are the hydrogenated A-B-A block copolymers ofstyrene-butadiene-styrene available under the KRATON® G trademark. Thesethermoplastic elastomers are especially attractive since they formblends with the norbornene-type polymers of this invention and aretransparent due to a very small (i.e., less than the wavelength ofvisible light) particle size morphology.

A further embodiment of this invention is a process and composition inwhich an elastomer containing either pendant unsaturation or end groupunsaturation is solution blended with norbornene-type monomer(s) in asuitable solvent (i.e., a solvent that dissolves the monomer and theelastomer but does not interfere with the subsequent polymerization).The norbornene-type monomer is then polymerized by addition of theabove-referenced catalyst systems. In this manner a chemical bond isformed between the growing norbornene polymer and the elastomer sincethe above described catalysts undergo a unique chain transfer reactionforming an A-B comb or di-block copolymer. This process is referred toherein as reactive in situ blending.

Examples of suitable elastomers include butadiene and isoprene rubber,allyl-terminated polyisobutylene, or ethylene/propylene (diene) rubber,siloxanes all of which can contain either pendant or end groupunsaturation. Another class of polymers having elastomeric propertieswhich are suitable for forming reactive in-situ blends with the PNB's ofthis invention are the A-B-A block copolymers ofstyrene-butadiene-styrene available under the KRATON® D trademark.Suitable unsaturation is defined by those carbon-carbon double bondswhich will undergo chain-transfer using the catalysts above described.The double bonds include vinyl groups and vinylidene groups.

A further embodiment of this invention is a process in which a terminalfunctional PNB macromonomer is copolymerized with an olefin using asuitable Ziegler-Natta catalyst systems to make an A-B comb blockcopolymer with pendant polynorbornene side blocks. A suitable terminalfunctional PNB includes vinyl-terminated PNB. In this case suitableolefin monomers include ethylene, propylene, butene, and longer chainalpha-olefins and mixtures thereof. Suitable Ziegler-Natta catalystsystems include titanium-based catalysts such as TiCl₃ in combinationwith diethylaluminum chloride, supported titanium catalysts such asTiCl₄ on MgCl₂ in combination with AlEt₃, vanadium catalysts such asVOCl_(3−x)(OR)_(x) (where x=0-3 and R is a hydrocarbyl substituent suchas methyl, ethyl, propyl, butyl, aryl, alkenyl, or alkaryl) incombination with AlR_(3−x)Cl_(x) (where x=0-2 and R is a hydrocarbylsubstituent such as methyl, ethyl, propyl, butyl, aryl, alkenyl, oralkaryl), or a metallocene-type catalyst in combination with amethaluminoxane cocatalyst or in combination with a trialkylaluminum andan activator. Suitable metallocene catalysts include those catalystsbased on Group IV metals (titanium, zirconium, and hafnium) containingone or two cyclopentadienyl ligands that can be unsubstituted,substituted, bridged or unbridged. Typical examples include but are notlimited to bis(cyclopentadienyl) zirconium dichloride, ethylene-bridgedbis(indenyl)zirconium dichloride, dimethylsilyl-bridgedbis(cyclopentadienyl) zirconium dichloride, and dimethylsilyl-bridgedbis(indenyl)zirconium dichloride. Suitable activators include strongneutral Lewis acids and ionic Brønsted acids. Examples of the formeractivators include, but are not limited to, tris(perfluorophenyl)boron,etc. Examples of the latter class of activators include, but are notlimited to N,N-dimethyl anilinium tetrakis(perfluorophenyl)borate andtrityl tetrakis(perfluorophenyl)borate, etc. The metallocene catalystsmay be used as unsupported or supported catalysts. Typical supportsinclude silica or alumina.

It is further contemplated within the scope of this invention thatpolynorbornenes containing isobutylene-terminal functionality react withisobutylene in the presence of a suitable cationic initiator to form acomb-type A-B block copolymer with polynorbornene pendant side blocks.Suitable cationic initiators include, but are not limited to, Lewisacids such as ethylaluminum dichloride, aluminum trichloride, borontrichloride, titanium tetrachloride, etc.

It is well known that polymers can be chlorinated. Examples ofcommercial chlorinated polymers include chlorinated polyethylene andchlorinated polyvinylchloride. Typically, these polymers are chlorinatedby addition of chlorine to the polymer in the presence of UV light orheat in solution, suspension, or in the solid state. Chlorinationimparts some desirable properties to the polymers. For example, in thecase of polyethylene, chlorination reduces the flammability of thematerial. In the case of polyvinylchloride, chlorination increases theglass transition temperature of the polymer as well as the commerciallyimportant heat distortion temperature. In addition to these properties,chlorination of the polymer changes its solubility characteristics andits compatibility with other polymers. Heretofore it has not beendemonstrated that PNB can be chlorinated. In this invention we haveshown that it is possible to chlorinate the polycyclic addition polymersof this invention and this is to be considered yet another embodiment ofthis invention. Chlorosulfonation of the polycyclic addition polymers isalso contemplated in this invention. Typically this is done by additionof chlorine and sulfur dioxide or addition of sulfuryl chloride to thePNB polymer in the presence of UV light or heat.

As outlined previously, one method of compatibilizing two polymers is toadd a random copolymer containing comonomer constituents that can formspecific interactions with the two or more polymers to be blended. Thistype of strategy can be followed for the polynorbornenes of the presentinvention. Thus, it is a further embodiment of this invention torandomly copolymerize norbornene with selected comonomers that willallow specific interactions with two or more selected polymers to formblends and/or alloys between the two or more selected polymers. Anexample of this type of strategy is exemplified by the copolymerizationof norbornene with 5-phenylnorbornene to form a random copolymer whichin turn can be mixed with any aryl-containing (co)polymer such aspolystyrene or polyα-methylstyrene. In this case the specificinteractions between polystyrene and the norbornene/5-phenylnorbornenecopolymer are characterized by π-π interactions between the phenyl groupof the aryl-containing polymer and the phenyl group of the5-phenylnorbornene of the norbornene copolymer. Another example mayinclude, but is not limited to, copolymerization of norbornene withacrylate-functional norbornenes to form blends with chlorinated polymerssuch as polyvinylchloride. In this case, the specific interactionsbetween the chlorinated polymers and the acrylate-functionalpolynorbornene is characterized as dipole-dipole. A further example mayinclude, but is not limited to, copolymerization of acid-functionalnorbornenes with norbornene followed by neutralization with a base suchas lithium or magnesium hydroxide to form blends with polyalkyleneoxides such as polyethylene oxide or polypropylene oxide. In this case,the specific interactions between the polyalkylene oxide and theneutralized acid-functional norbornene copolymer is characterized asion-dipole.

It is well known to those skilled in the art that maleic anhydridegrafting onto polyolefins, such as polyethylene and propylene, is oftenperformed to improve physicochemical properties of typically hydrophobicpolymers to promote adhesion, dyability, and to provide functionalityfor other chemical modifications (see B. C. Triveldi and B. M.Culbertson, Maleic Anhydride, Plenum Press, New York, 1982). Thegrafting is typically accomplished using mechanochemical (such asextrusion), mechanochemical with free-radical initiators, free radical,ionic, and radiation-initiation techniques. Depending on the chemicalnature of the polymer to be grafted a free radical, “ene” (indirectsubstituting addition), or Diels Alder reaction route may be employed.Grafting of maleic anhydride onto polyethylene and polypropylene usingsolution free radical methods typically use xylene as a solvent andbenzoyl peroxide as an initiator and take place between 90° and 130° C.,or use refluxing chlorobenzene (or dichlorobenzene) with benzoylperoxide, t-butyl peroxybenzoate, or di-t-butyl peroxide. Literaturealso shows the subsequent reaction with amines produced detergentadditives for lubricants (Shell International, Netherland Patent No.2,969 (1965)). Typically the grafted maleic anhydride content is between0.1 and 5 wt. %. Extrusion grafting typically occurs at typical meltextrusion temperatures for polyethylene and polypropylene (T>200° C.)and may also occur in the presence of a free radical initiator. It hasbeen observed that maleic anhydride grafted polypropylene has shown anincreased dispersability with Nylon 6 (F. Ide and A. Hasegawa, J. Appl.Polym. Sci., 18(4), 963 (1974)) through reaction of the maleic anhydridemoiety on the polypropylene with the nylon amino residues. Grafting hasbeen shown to occur for a variety of polymers including polyethylene,polypropylene, ethylene propylene copolymers, polystyrene,polyvinylchloride, polyisobutylene, polyvinylacetals, polyisoprene,polybutadiene, polytetrafluoroethylene, polyacrylates, otherpoly-alpha-olefins and polymers containing furfuryl residues.

To our knowledge norbornene-type addition polymers have heretofore neverbeen synthesized. We have found that the homo- and copolymeric PNBs ofthis invention can be reacted (through a free radical mechanism) withmaleic anhydride to form grafts of succinic anhydride. The PNB/succinicanhydride graft copolymers thus prepared can be further reacted with avariety of moieties that contain coreactive functionalities withsuccinic anhydride.

The polycyclic polymers may be grafted with an unsaturated carboxylicacid or a derivative thereof. Examples of the unsaturated carboxylicacid used herein include acrylic acid, maleic acid, fumaric acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,isocrotonic acid and nadic acid (endocisbicyclo [2,2,1]hept-5-ene-2,3-dicarboxylic acid). The derivatives of theabove-mentioned unsaturated carboxylic acids are unsaturated carboxylicacid anhydrides, unsaturated carboxylic acid halides, unsaturatedcarboxylic acid amides, unsaturated carboxylic acid imides and estercompounds of unsaturated carboxylic acids. Concrete examples of thesederivatives include maleyl chloride, maleimide, maleic anhydride,citraconic anhydride, monomethyl maleate, dimethyl maleate and glycidylmaleate.

These graft monomers exemplified above may be used either singly or incombination.

Of the above-exemplified graft monomers, preferred are unsaturateddicarboxylic acids or derivaties thereof, and particularly preferred aremaleic acid and nadic acid or acid anhydrides thereof.

The PNB/succinic anhydride graft copolymers of this invention can beprepared by dissolving the PNB and maleic anhydride in an appropriatesolvent. Suitable solvents such as hydrocarbons, halohydrocarbons,aromatics and haloaromatics, preferred solvents are the aromatics andhaloaromatics such as toluene, xylene, benzene, chlorobenzene, ando-dichlorobenzene. The reaction solution is then a sufficient amount ofa suitable peroxide initiator. Suitable initiators include organicperoxides such as lauroyl peroxide, benzoyl peroxide, diacetyl peroxide,5-butyl-peroxyneodeconate, t-butylcumyl peroxyneodecanoate, di-n-propylperoxydicarbonate, and di-sec-butyl-peroxydicarbonate. The maleicanhydride is employed in an amount of up to about 10 percent by weightof the PNB polymer. Preferably maleic anhydride is utilized in the rangeof from about 0.1 to 5 percent by weight of the PNB polymer. Thegrafting reaction is conducted in a temperature range from about 120° C.to 220° C., preferably from 140° C. to 200° C., and most preferable from160° C. to 180° C.

The PNB/succinic anhydride graft copolymers can be further reacted withpolyamides, particularly, amine terminated polyamides, such as, forexample, Nylon 66, Nylon 12, and Nylon 6. The PNB/MA-polyamide graftcopolymer can be formed from solution or reactive extrusion.

In the solution process the PNB/MA graft copolymer and the polyamide(nylon) are dissolved in an appropriate solvent or mixture of solvents.The reaction medium is heated at a temperature range from about 20° C.to about 200° C., preferably about 130° C.

In the melt process the maleic anhydride, PNB polymer, and polyamidecomponents can be reactive processed on an extruder, mill or any of thewell known thermal mechanical mixing devices commonly used in theplastic compounding industry. The components react in the melt to give aPNB/succinic anhydride/polyamide graft copolymer. The temperatureemployed should be above the T_(g) of the PNB, but of course should bebelow the degradation temperature of the PNB. It will be understood thatdifferent homo- and copolymers of PNB will have differing T_(g)'s anddegradation temperatures. Typically, the temperature range employed canbe from about 150° C. to about 350° C.

Other polymer resins such as amine terminated silicones, amineterminated polypropylene oxides, and amine terminated polybutadienes canbe coreacted with the PNB/succinic anhydride graft copolymers of thisinvention, in a similar manner as discussed hereinabove.

As discussed above any functionality that is reactive with thePNB/succinic anhydride functionality can be coreacted therewith toprepare novel PNB graft copolymers. Exemplary of the coreactivefunctional groups that can be reacted on the PNB backbone are asfollows:

Coreactive functionality Linkage 1. Amines → amic acid and imide A.Primary amines: a) ethylene diamine b) diethylene triamine c)triethylene tetramine d) dimethylamino propylamine e) diethylaminopropylamine B. Secondary amines (mono, di and poly) a) cycloaliphaticprimary amines b) cycloaliphatic secondary amines c) cycloaliphaticpolyamines d) mono, bis and poly (hydroxyethyl) diethylene triaminesamines e) aromatic amines f) poly(oxypropylene diamine) g)poly(oxypropylene triamine) h) poly(glycol amines) i) diamine terminatedpoly(arylene ether sulfones) j) diamine terminated poly(arylene etherketones) k) mono and diamine terminated polyamides 2. Alcohols → monoand diesters A. aliphatic alcohols (mono and di) B. aromatic alcohols(mono and di) 3. Thiols → mono and di thio esters A. aliphaticmercaptans (mono and di) B. aromatic thiols (mono and di) 4. Water →diacid

The following examples will show one skilled in the art how to operatethe scope of the present invention and are not intended to serve as alimitation on the scope hereof.

EXAMPLE 1 Synthesis of Vinyl-terminated PNB Copolymer ofNorbornene/decylnorbornene Copolymer

Norbornene (82.5 g) and 5-decylnorbornene (27.5 g) were dissolved in1.17 l of dried dichloroethane. This mixture was degassed and added to a2 l stainless steel reactor. The mixture was cooled to 10° C. andsaturated with ethylene at 125 psig. A dichloroethane solution of[(crotyl)Ni(COD)][PF₆] (0.091 g) was added to the mixture. The reactionwas allowed to continue for 1.25 h. The reaction was terminated byreleasing the ethylene pressure and injecting ethanol into the reactor.The polymer was isolated by pouring the reaction mixture into ethanol,filtered, and dried (yield 38.5 g). The molecular weight of the isolatedpolymer was determined by GPC: M_(w)=4750 and M_(n)=3000. NMR analysisof the material showed that it contained vinyl end groups withresonances at about 5.7 (1 H) and 4.7 ppm (2 H).

EXAMPLE 2 Synthesis of Vinyl-terminated PNB Homopolymer

Norbornene (150 g) was dissolved in 1500 ml of dried dichloroethane.This mixture was degassed and added to a 2 l stainless steel reactor.The mixture was cooled to 10° C. and saturated with ethylene at 250psig. A dichloroethane solution of [(crotyl)Ni(COD)][PF₆] (0.146 g) wasadded to the mixture. Within 10-15 min, the reaction exothermed to atleast 80° C. After terminating the reaction, considerable polymer hadprecipitated and was isolated by filtration, then dried (yield 55.4 g,fraction −1). The filtrate was added to MeOH and more precipitate formed(yield 38.3 g, fraction −2). This filtrate was then added to more MeOHand yet more precipitate formed (yield 11.2 g, fraction −3). Eachfraction was determined by proton NMR to contain vinyl end groups. Themolecular weight of each fraction was also determined by GPC: fraction−1: M_(w)=3080 and M_(n)=1800; fraction −2: M_(w)=1660 and M_(n)=1250;fraction −3: M_(w)=970 and M_(n)=820.

EXAMPLE 3 Synthesis of an Isobutylene-terminated PNB

The isobutylene-terminated polynorbornene was synthesized in thefollowing manner. Norbornene (5 g) was added to a 100 ml vial equippedwith a stir bar, then crimp capped with a septum. To this was added 50ml of dried dichloroethane. The solution was degassed, cooled to −30° C.and isobutylene (5.0 g) was added. To this solution was added 0.01 mlnickel (II) ethylhexanoate (8% Ni) followed by 1 ml of 0.125M solutionof N,N-dimethylanilinium tetraperfluorophenyl borate in dichloroethaneand 0.38 ml of a 1.7M solution of triethylaluminum in toluene. Themixture was stirred for an hour at −30° C. The resulting slurry waspoured into MeOH, filtered, and dried at 80° C. under vacuum overnight.Yield 4.6 g. GPC: M_(w)=9800, M_(n)=4200.

EXAMPLE 4 Formation of Alcohol-terminated PNB Copolymer ofNorbornene/decylnorbornene

Into a round bottom flask was added 1.0 g of a vinyl-terminatednorbornene/decylnorbornene copolymer (from Example 1). This wasdissolved in 50 ml of dried, degassed THF. To this mixture was added 6.7ml of a 0.5M THF solution of 9-borobicyclo[3.3.1]nonane (9-BBN). Thesolution was refluxed for 1.5 h under an Ar atmosphere and cooledovernight. Water (5 ml) was carefully added to the flask. Another 5 mlof NaOH (3M in water) was added followed by 20 ml hydrogen peroxide(30%). The solution was transferred to a separator funnel and washedwith a saturated aqueous solution of K₂CO₃ (10 ml). The THF layer wasseparated from the aqueous layer and the polymer was isolated from theTHF layer by precipitation into MeOH. The polymer was dried at 80° C.under vacuum. The formation of an alcohol-terminatednorbornene/decylnorbornene copolymer was confirmed by ¹H NMRspectroscopy. The methylene resonances adjacent to the terminal hydroxylfunctionality resonate at 3.7 ppm. These assignment of these resonanceswas confirmed by reaction with Cl₃CNCO which yielded an upfield shift to4.2 ppm.

EXAMPLE 5 Formation of Alcohol-terminated Norbornene Homopolymer

Into a round bottom flask was added 10 g of a vinyl-terminatednorbornene homopolymer (from Example 2). This was dissolved in 150 ml ofdried, degassed THF. To this mixture was added 61.2 ml of a 0.5M THFsolution of 9-borobicyclo[3.3.1]nonane (9-BBN). The solution wasrefluxed for 1.5 h under an argon atmosphere and cooled overnight. Water(25 ml) was carefully added to the flask. Another 25 ml of NaOH (3M inwater) was added followed by 60 ml of hydrogen peroxide (30%). More THFwas added until two layers formed. The solution was transferred to aseparator funnel and washed with a saturated aqueous solution of K₂CO₃(150 ml). The mixture was allowed to separate over several hours. TheTHF layer was separated from the aqueous layer and the polymer wasisolated by precipitation into MeOH (1000 ml). The polymer was filteredand dried at 80° C. under vacuum. The formation of an alcohol-terminatednorbornene homopolymer was confirmed by ¹H NMR spectroscopy. Themethylene protons adjacent to the terminal hydroxyl group resonate at3.7 ppm.

EXAMPLE 6

This example shows that maleic anhydride can be incorporated on the endof an isobutylene-terminated PNB to give an allyl succinic anhydrideterminal functionality.

Formation of an allyl succinic anhydride-terminated PNB by reaction of aisobutylene-terminated PNB with maleic anhydride. Anisobutylene-terminated polynorbornene (0.050 g) and maleic anhydride(0.0012 g) were dissolved in deuterated ortho-dichlorobenzene, placedinto an NMR tube and heated to 200° C. overnight. The vinylidene protonresonances of the isobutylene-terminated polynorbornene were replaced byprotons of the allyl succinic anhydride group (5.30 and 5.15 ppm).

EXAMPLE 7 Formation of an Aldehyde-terminated PNB from theHydroformylation of an Isobutylene-terminated PNB

Isobutylene-terminated polynorbornene (from Example 3) (1.0 g) wasdissolved in 20 ml of toluene and then degassed with argon. Irgafos,(P(O(2,5-t-Bu)C₆H₃)₃, (0.06 g) and [Rh(1,5-COD)(acetate)]₂ (0.0023 g)were each dissolved in 10 ml dried, degassed toluene. The threesolutions were then transferred into a stainless steel reactor. Thereactor was pressurized with 300 psig synthesis gas (equimolar CO andH₂) and heated to 80° C. The reactor was vented and repressurized forthe first 3-4 h. The reaction was continued for 48 h. After cooling, a 5ml aliquot of the resulting golden brown solution was poured intoacetone to precipitate the polymer. The white powder was filtered anddried. IR analysis of the polymer indicated the formation of an aldehydeend group since a CO stretch was observed at about 1660 cm⁻¹.

EXAMPLE 8 Synthesis of Epoxy-terminal PNB

Vinyl-terminated PNB (fraction 1 from Example 2, above) (20 g) wasdissolved in toluene (100 ml). To this mixture was added3-chloroperoxybenzoic acid (11.4 g). After stirring the mixture, thepolymer was precipitated into MeOH. Proton NMR analysis of the resultingpolymer, showed no vinyl resonances present. New resonances appeared at2.8 to 3.0 ppm and are assigned to those protons adjacent to the epoxidefunctionality.

EXAMPLE 9

This example exemplifies the reaction of alcohol-terminated PNB with theisocyanate MDI (methylene diphenyl diisocyanate) as a reaction forincorporation of the alcohol-terminated PNB into a polyurethaneformulation.

Reaction of an Alcohol-terminated PNB with MDI

Two equivalents of an alcohol-terminated norbornene/decylnorbornenecopolymer (from Example 2) were reacted with MDI (0.02 g, MW=250) indeuterated-tetrachloroethane in an NMR tube for 1 h at 80° C. Formationof a urethane linkage was confirmed by ¹H NMR spectroscopy; themethylene protons adjacent to the hydroxy-end group shifted from 3.7 ppmto 4.2 ppm.

EXAMPLE 10 Reaction of an Epoxy-terminated PNB with a DifunctionalAcid-terminated Polybutadiene (A-B-A block copolymer)

Epoxy-terminated PNB (0.03 g, from Example 7) and carboxylicacid-terminated polybutadiene (HYCAR® CTB 2000X 162, 0.052 g,M_(w)=2375) was dissolved in 30 ml of toluene. The solution was degassedwith argon. To this solution was added 8.5 microliters of1,8-diazabicyclo[5.4.0]undec-7-ene as a catalyst. The mixture was heatedto 80° for 24 hours. From ¹H NMR analysis of the product, it wasapparent that the epoxy functionality had reacted; the intensity ofprotons of the epoxide at 2.85 ppm decreased markedly and was replacedby new signals at 3.40 ppm. These signals are assigned to the methyleneprotons vicinal to the hydroxy and the ester functionality.

EXAMPLE 10A Reaction of an Epoxy-terminated PNB with a DifunctionalAcid-terminated Polybutadiene (ABA Block Copolymer)

Epoxy-terminated PNB (0.2 g, from Example 8) and carboxylicacid-terminated polybutadiene (HYCAR® CTB 2000X 162, 0.20 g, M_(w)=2375)was dissolved in 30 ml of toluene. The solution was degassed with argon.To this solution was added 1.7 microliters of1,8-diazabicyclo[5.4.0]undec-7-ene as a catalyst. The mixture was heatedto 80° C. overnight. From ¹H NMR analysis of the product, it wasapparent that the epoxy functionality had reacted; the intensity ofprotons of the epoxide at 2.85 ppm decreased markedly and was replacedby new signals at 3.4-3.5 ppm. These signals are assigned to themethylene protons vicinal to the hydroxy and the ester functionality.

EXAMPLE 11 Control Experiment for Example 13

Norbornene polymerization in absence of chain transfer agent.

Norbornene (2.0 g) was dissolved in 30 ml of dichloroethane. Thesolution was degassed with argon. To this solution was added[(crotyl)Ni(COD)]PF₆ (0.0039 g). The polymerization was allowed to runfor one hour and then was terminated by addition to MeOH. The polymerwas isolated by pouring the reaction mixture into an excess of MeOH. Theresulting solid was filtered and dried. Yield 1.62 g. GPC analysis ofthe product showed an M_(w)=1,270,000 and M_(n)=558,000.

EXAMPLES 12-13

These examples show the utility of an allyl-terminated macromolecule(namely polyisobutylene) as a chain-transfer agent and as a coreactantto make A-B block copolymers.

EXAMPLE 12 Synthesis of Allyl-terminated Polyisobutylene (PIB)

Hexane (70 g) and methylchloride (70 g) were transferred to a reactionvessel and cooled with a dry ice/isopropanol bath.2,6-di-tert-butylpyridine (0.5 ml), 2,4,4,-trimethyl-2-chloropentane(0.23 g), and titanium tetrachloride (3.29 g) were added to the reactionflask. Isobutylene (16 g) was transferred to the reaction vessel. Themixture was stirred for 30 min after which time pre-chilledallyltrimethylsilane (3.5 g) was added and stirred for an additional 30min. The vessel contents were then poured into saturated aqueous sodiumbicarbonate and the volatiles were allowed to evaporate. The organiclayer was separated and washed three times with water. The polymer wasprecipitated into acetone. The acetone was decanted and the residue wasdissolved in hexane. The hexane was removed in vacuo to yield a solid.Yield 15.2 g. GPC determined the M_(w) to be 16,000 and M_(n) to be14,500.

EXAMPLE 13 Synthesis of PNB-PIB Block Copolymer

Allyl-terminated polyisobutylene (2.6 g, from synthesis above) andnorbornene (2 g) was dissolved in 30 ml of dichloroethane. The solutionwas degassed with argon. To this solution was added [(crotyl)Ni(COD)]PF₆(0.0039 g). The polymerization was allowed to run for one hour and thenwas terminated by addition to MeOH. The polymer was isolated by pouringthe reaction mixture into an excess of MeOH. The resulting solid wasfiltered and dried. Yield 2.87 g. The GPC trace was bimodal:M_(w)=17,300, M_(n)=15,900 and M_(w)=300,000, M_(n)=169,000. Based onthe values of the lower molecular weight fraction, this material isunreacted allyl-terminated PIB.

The polymer product was subjected to Soxhlet extraction using methylenechloride solvent. The soluble portion was found to be unreactedallyl-terminated polyisobutylene by NMR. The insoluble portion was foundto contain polyisobutylene and polynorbornene resonances by NMR, but noallyl end groups were present indicating that a block copolymer wasformed. The GPC molecular weight of the methylene chloride insolubleportion gave an M_(w)=345,000 and an M_(n)=164,000. The lower molecularweight of this material, relative to the control PNB (Example 11), isconsistent with the allyl-terminated PIB being a macromolecular chaintransfer agent.

EXAMPLE 14

The following example exemplifies the synthesis of PNB copolymerscontaining pendant unsaturation.

All reactions were carried out in glass flasks under an inert atmosphereusing dried and degassed dichloroethane. Dichloroethane was added to thereaction flask, followed by the monomers set forth in the table below.The reaction mixture was degassed with nitrogen. The nickel (II)ethylhexanoate catalyst was added as a solution in dichloroethane. Thenthe trialkylaluminum cocatalyst (either triethyl- ortriisobutyl-aluminum) was added as a toluene solution. Then neathexachloroacetone was added to the mixture. The reaction was carried outfor approximately 1 hour. MeOH (typically 5 ml) was added to terminatedthe reaction. The mixture was then added to an excess of MeOH (typicallya 3:1 ratio) to isolate the polymer. The polymer was then filtered,washed with MeOH, and dried. See the table below for details of eachpolymerization run.

Experiment [NB] [Comonomer]* Monomers:Ni Ni:Al:H Conv Mw Mn No. (g) (g)(molar) CA** (%) (×10⁻³) (×10⁻³) Comments 1 136 ENB(58) 2500:1 1:10:1050 136 35 Al = triisobutylaluminum 2 85 ENB(109) 2500:1 ″ 35 94.5 24 ″ 3136 ENB(58) 2500:1 ″ 61 129 32 ″ 4 136 ENB(58) 2500:1 ″ 54 107 33 ″ 5183 — 2500:1 ″ 80 100 45.7 Al = triethylaluminum 6 85 ENB(109) 2500:1 ″24 70 19.1 Al = triisobutylaluminum 7 136 ENB(58¹) 2500:1 ″ 67 61 21 ″ 885 ENB(109¹) 2500:1 ″ 31 45 19 ″ 9 136 ENB(58) 2500:1 ″ 50 145 36 ″ 1085 ENB(109) 2500:1 ″ 26 61 18.4 ″ 11 136 ENB(58²) 2500:1 ″ 54 124 30 ″12 85 ENB(109²) 2500:1 ″ 30 45 19 ″ *ENB = ethylidene norbornene ¹= with3 mol % decene-1 relative to monomers ²= with 1 mol % decene-1 relativeto monomers **= HCA = hexachloroactone

EXAMPLE 15

The following example exemplifies the synthesis of PNB copolymerscontaining pendant unsaturation.

Preparation of Nickel Catalyst

In the dry box, 0.2 ml of HSbF₆ is added to a dried Teflon® vial. Thevial is cooled. An equimolar amount of nickel (II) ethylhexanoate (3.15ml, 8 wt % Ni) is added to the vial, warmed to room temperature andstirred for 2 hours. The mixture is stored at −20° C. before use.

Polymerization Procedure

All reactions were carried out in glass flasks under an inert atmosphereusing dried and degassed dichloroethane. Dichloroethane was added to thereaction flask, followed by the monomers set forth in the table below.The reaction mixture was degassed with nitrogen. The nickel catalyst (asprepared above) was added to the mixture. Then BF₃.Et₂O, followed bytriethylaluminum in toluene solution. The reaction was carried out forapproximately 1 hour. MeOH (typically 5 ml) was added to terminated thereaction. The mixture was then added to an excess of MeOH (typically a3:1 ratio) to isolate the polymer. The polymer was then filtered, washedwith MeOH, and dried.

Experiment [NB] [Comonomer]* Monomers:Ni Conv Mw Mn No. (g) (g) (molar)Ni:Sb:B:Al (%) (×10⁻³) (×10⁻³) Comments 1 decyl-NB, 186 4000:1 1:1:9:1058 — — Al = triethylaluminum 2 85 VNB, 109 ″ ″ 3 6.2 3 ″ 3 82 DCPD, 116″ ″ 18 92 13.3 ″ 4 82 DCPD, 116² ″ ″ 27 — — ″ 5 2.5 CyNB, 4.6 ″ ″ 28 — —″ *VNB = vinyl norbornene, DCPD = dicyclopentadiene, CyNB =cyclohexenylnorbornene ²with 1 mol % decene-1 relative to monomers

EXAMPLE 16

This example demonstrates the epoxidation of terminal and pendantunsaturated groups of PNB polymers.

Epoxidation Procedure

The polymers listed in the table below were dissolved in toluene(typically 10 wt %). (If needed, an equal amount of chloroform was addedto the mixture to aid in solubility.) Typically, a 1.1 molar ratio of3-chloroperoxybenzoic acid (50%) to the number of double bonds in thepolymer was added to the toluene solution. The reaction was allowed tocontinue stirring overnight. The polymer was isolated by pouring thereaction mixture to an excess of MeOH, filtered, washed with additionalMeOH, and dried. If by NMR assay showed incomplete epoxidation hasoccurred, the epoxidation is carried out once again as described above.Determination of full epoxidation relies on disappearance of the doublebond resonances associated with the incorporated diene monomer (ENB:4.8-5.5 ppm; VNB: 4.8-6.0 ppm; DCPD: 5.5-6.0 ppm; CyNB: 5.4-5.7 ppm) orthe vinyl-terminated polymers (approximately 5.5-6.0 and 4.8-5.0 ppm).If m-chloro benzoic acid impurities are present in the polymer (asdetermined by NMR), the polymer is reprecipitated from toluene solutionwith MeOH until no residual m-chloro benzoic acid is detectable by NMR.

Experiment No. Polymer Starting Material M_(w)(×10⁻³) M_(n)(×10⁻³) 1VT-NB + NB10 — — 2 NB/ENB 50/50 60 20 3 NB/ENB 75.25 113 39 4 DT-NB/ENB75/25 63 17 5 VT-PNB 3.5 2.3 6 DT-NB/ENB 50/50 45 22 7 DT-NB/ENB 75/25165 46 8 NB/ENB 50/50 52 17.5 9 DT-NB/ENB 50/50 44 18.3 10 VT-PNB 7 3.911 NB/VNB 50/50 7.9 4.9 12 NB/DCPD 50/50 — — 13 NB/CyNB 50/50 75.1 20.8VT = vinyl terminated NB = norbornene ENB = ethylidene norbornene DT =decenyl terminated NB10 = decyl norbornene DCPD = dicyclopentadiene CyNB= cyclohexyl norbornene

EXAMPLE 17

These examples show that the polymers made in Example 12 above can findutility in blends with CPVC.

Solution blends of CPVC and epoxidized PNB copolymers (containingterminal and pendent epoxy groups) were prepared in a mixed solventsystem of 1,2-dichloroethane/THF (2:1 v/v). A 2.0% by weight solution ofthe blend compositions was prepared and warmed to 50° C. overnight toinsure complete dissolution and mixing of components. Solution blends ofCPVC and epoxidized vinyl-terminated norbornene polymers were preparedin a mixed solvent system of THF/cyclohexane (1:1 v/v). A 2.0% by weightsolution of the blend compositions was prepared and warmed to 50° C.overnight to insure complete dissolution and mixing of components.

Solvent-cast films used for evaluation were prepared by applying threecoats of the solutions onto clean glass microscope slides with an eyedropper. Films were then dried in an air oven at 60° C. for 2 hours.Further drying, to remove residual solvent, was done by placing theslides in a vacuum oven at 80° C. overnight.

Blend morphology was determined using both light and scanning electronmicroscopic techniques. Light micrographs were obtained at 700×magnification and SEM at 2,500× and 1,000× magnification.

Blends of CPVC (I.V.=0.68) with epoxidized NB/ENB obtained from Example16, experiment 2, copolymer (50/50).

The results are set forth in the table below:

Experiment Blend Ratio (67% Light SEM No. CPVC*F-PNB) MicroscopyObservation 1 100/0  1 phase 1 phase 2 80/20 1 phase 1 phase 3 50/50 1phase 1 phase 4 20/80 1 phase 1 phase 5  0/100 1 phase 1 phase F-PNB =functional PNB *67% chlorine by wt.

Experiment Blend Ratio (67% Light SEM No. CPVC*F-PNB) MicroscopyObservation 1 100/0  1 phase 1 phase 2 80/20 1 phase 1 phase 3 50/50 1phase 1 phase 4 20/80 1 phase 1 phase 5  0/100 1 phase 1 phase F-PNB =functional PNB *67% chlorine by wt.

EXAMPLE 18

Blends of CPVC (I.V.=0.68) with epoxidized vinyl-terminatedpolynorbornene obtained from Example 16, experiment 10. Solution blendsof CPVC and epoxidized PNB copolymers were prepared and tested as inExample 17. The results are set forth in the table below:

Experiment Blend Ratio (67% Light SEM No. CPVC*F-PNB) MicroscopyObservation 1 100/0  1 phase 1 phase 2  0/100 1 phase 1 phase 3 98/2  1phase — 4 96/4  1 phase — 5 90/10 1 phase — 6 70/30 2 phase 2 phase 750/50 2 phase 2 phase *F-PNB = functional PNB *67% chlorine by wt.

EXAMPLE 19

Blends of CPVC (I.V.=0.68) with epoxidized NB/DCPD copolymer (50/50)obtained from Example 16, experiment 12. Solution blends of CPVC andepoxidized PNB copolymers were prepared and tested as in Example 17. Theresults are set forth in the table below:

Experiment Blend Ratio (67% Light SEM No CPVC*F-PNB) MicroscopyObservation 1 100/0  1 phase — 2 80/20 1 phase — 3 50/50 1 phase — 420/80 2 phase 2 phase 5  0/100 1 phase 1 phase   coarse F-PNB =functional PNB *67% chlorine by wt.

EXAMPLE 20

Blends of CPVC (I.V.=0.68) with epoxidized NB/VNB copolymer (50/50)obtained from Example 16, experiment 11. Solution blends of CPVC andepoxidized PNB copolymers were prepared and tested as in Example 17. Theresults are set forth in the table below:

Experiment Blend Ratio (67% Light SEM No. CPVC*F-PNB) MicroscopyObservation 1 80/20 1 phase — 2 70/30 1 phase — 3 50/50 1 phase 1 phase4  0/100 1 phase 1 phase F-PNB = functional PNB *67% chlorine by wt.

EXAMPLE 21

This example demonstrates the free radical grafting of a vinyl-typepolymer onto a non-functional PNB.

Into a two necked, 100 ml round bottom flask fitted with a overheadmechanical stirrer and an argon inlet, 1.0 g (5×10⁻⁶ moles) ofpolynorbornene (M_(w)=200,000 g/mole) was added under argon atmosphere.To this 9.0 g (0.086 moles) of freshly distilled styrene and 0.05 g ofdi t-butyl peroxide were added. The solution was diluted with 10 ml ofchlorobenzene, stirred until all the PNB had dissolved and slowly heatedto about 120° C. The reaction was stirred for about 5 hours, duringwhich time the solution's viscosity was observed to increaseconsiderably. After 5 hours, the polymer solution was cooled, dilutedwith toluene and precipitated into methanol to obtain a white polymer,which was dried at 100° C. in a vacuum oven. In order to obtaininformation on the grafting efficiency, pure graft copolymers had to beisolated. It was found that by dissolving part of these samples,followed by centrifuging the samples, PNB graft copolymers can beseparated from polystyrene homopolymers, as the PNB graft copolymer isnot soluble in tetrahydrofuran while the polystyrene was. Suchextraction of the graft samples were performed three times on all thesamples. ¹H NMR analysis of the tetrahydrofuran insoluble polymerindicated the presence of aromatic protons at 6.4 ppm and 7.2 ppmcorresponding to the polystyrene and broad aliphatic protons appearingaround 1-2.5 ppm corresponding to the norbornene polymer. Also films ofthe tetrahydrofuran insoluble material, cast from cyclohexane wereobserved to be clear and transparent. The clear film obtained from thetetrahydrofuran insoluble material followed by the presence of styreneprotons from proton NMR are a clear evidence for grafting of styrene onto polynorbornene polymers.

EXAMPLE 22

This example demonstrates the free radical grafting of a vinyl-typepolymer onto a PNB having pendant unsaturation.

Into a two necked, 100 ml round bottom flask fitted with a magneticstirrer and an argon inlet, 4.55 g (0.189 mmoles) ofpolynorbornene/ethylidene norbornene (PNB/ENB) copolymer containing 50mole % of ethylidene norbornene was added under argon atmosphere. Tothis 13.6 g (0.131 moles) of freshly distilled styrene and 5.9 mg (0.029mmoles) of dodecanethiol were added. The solution was further dilutedwith 5 ml of chlorobenzene and stirred until all the PNB/ENB copolymerhad dissolved. The solution was slowly heated to about 120° C. at whichpoint 0.018 g (0.066 mmoles) of dicumyl peroxide was added. After theaddition of the peroxide the solutions viscosity was observed toincrease and after about 3 hours the viscosity of the solution was sohigh that stirring was observed to be difficult. The reaction wasstopped, diluted with toluene and precipitated into methanol to obtain awhite polymer, which was dried at 60° C. in a vacuum oven. ¹H NMRanalysis of the polymer indicated the presence of aromatic protons at6.4 ppm and 7.2 ppm corresponding to the polystyrene and broad aliphaticprotons appearing around 1-2.5 ppm corresponding to the norbornenepolymer. A small sample of the polymer was dissolved in chlorobenzeneand films casted from the solution was observed to be clear. It is to benoted that film cast from chlorobenzene of high molecular weightpolystyrene and polynorbornene polymers were observed to be opaqueindicating phase separated morphology. The appearance of the clear filmin the case of polymerization of styrene in the presence of PNB/ENBcopolymer indicates that styrene is grafting on to PNB/ENB copolymer.

EXAMPLE 23

This example illustrates the free radical polymerization of a vinyl-typemonomer in the presence of a PNB and polymeric impact modifier.

Into a two necked, 100 ml round bottom flask fitted with a overheadmechanical stirrer and an argon inlet, 1.0 g (5×10⁻⁶ moles) ofpolynorbornene M_(w)=200,000 g/mole was added under argon atmosphere. Tothis 4.5 g (0.043 moles) of freshly distilled styrene and 0.3 g ofstyrene butadiene styrene copolymer (Cariflex® TR 1102) was added. Thesolution was diluted with 10 ml of chlorobenzene, stirred until all thePNB had dissolved and slowly heated to about 90° C. The reaction wasstirred for about 12 hours, during which time the solutions viscositywas observed to increase considerably. After 12 hours, 0.05 g of dit-butyl peroxide was added followed by another 4.5 g of styrene monomerto the reaction flask. The flask was further heated to 150° C. for 3hours, cooled, further diluted with toluene and precipitated intomethanol to obtain a white polymer, which was dried at 100° C. in avacuum oven. Films cast from the rubber modified material was observedto be translucent indicating phase separated morphology.

These Examples illustrate in situ blends of PNB polymers with reactiveand unreactive elastomers.

EXAMPLE 24 Copolymerization of Norbornene and 5-decylnorbornene toGenerate in Situ Blend with KRATON® G 1652

To a 50 ml glass vial containing a magnetic stir bar and a mixture ofnorbornene and 5-decylnorbornene (75/25 mol/mol, 53 mmol totalnorbornenes) was added cyclohexane containing varying levels of adissolved rubber (KRATON® G 1652, the solution having been dried overmolecular sieves and purged with nitrogen) followed by nickelethylhexanoate (0.013 mmol) and ethylaluminum dichloride (0.065 mmol).After one hour ethanol was injected to the solution to terminate thereaction. The polymer blend was then precipitated with excess ethanoland was washed with excess acetone, filtered and dried overnight, undervacuum at 80° C. The polymer yields are tabulated below:

Yield of polynor- bornene Cyclo- Total (total hexane, Rubber, yield,rubber), ml. g g g M_(w) M_(n) Comments 35 1.5 7.1 5.6 327,000 104,000bimodal MWD (shoulder) 17.5 0.75 6.5 5.75 292,000 109,000 bimodal MWD(shoulder)

EXAMPLE 25 Homopolymerization of Norbornene to Generate in Situ Blendwith KRATON® G 1652

To a 50 ml glass vial containing a magnetic stir bar and norbornene (5g, 53.1 mmol) was added cyclohexane containing varying levels of adissolved rubber (KRATON® G 1652, the solution having been dried overmolecular sieves and purged with nitrogen) followed by nickelethylhexanoate (0.013 mmol) and ethylaluminum dichloride (0.065 mmol).After one hour ethanol was injected to the solution to terminate thereaction. The polymer blend was then precipitated with excess ethanoland was washed with excess acetone, filtered and dried overnight, undervacuum at 80° C. The polymer yields are tabulated below:

Yield of polynor- bornene Cyclo- Total (total- hexane, Rubber, yield,rubber), ml. g g g M_(w) M_(n) Comments 7.5 0.3 5.2 4.9 272,000 79,00035 1.5 6.3 4.8 393,000 75,900 bimodal MWD (shoulder)

EXAMPLE 26

This example demonstrates using a polymer with pendant vinyl groups aschain transfer agent by dissolving the polymer in the hydrocarbonpolymerization medium and running a solution and/or suspensionpolymerization to give a graft copolymer.

Polymerization of norbornene in the presence of polybutadiene togenerate in situ grafts, as well as to control molecular weight.

To a 50 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 20 ml dichloroethane and 11 g of a 9.1weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in dichloroethane (that had been dried over molecularsieves and purged with nitrogen) followed by catalyst component “A” (seeExample 35) (0.013 mmol), BF₃.etherate (0.117 mmol) and triethylaluminum(0.130 mmol). After one hour ethanol was injected to the solution toterminate the reaction. The polymer was then precipitated with excessethanol and was washed with excess acetone, filtered and driedovernight, under vacuum at 80° C. The polymer was isolated in 85% yield(5.1 g). GPC methods revealed the graft copolymer to possess an M_(n) of32,000 and an M_(w) of 59,000.

Comparative Experiment

This control experiment was run under similar conditions to the aboveillustrative example except that the experiment was run in the absenceof the polybutadiene, resulting in no chain transfer or grafting and anextremely high molecular weight.

To a 100 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 80 ml dichloroethane followed by catalystcomponent “A” (see Example 35) (0.026 mmol), BF₃.etherate (0.234 mmol)and triethylaluminum (0.260 mmol). After one hour ethanol was injectedto the solution to terminate the reaction. The polymer was thenprecipitated with excess ethanol and was washed with excess acetone,filtered and dried overnight, under vacuum at 80° C. The polymer wasisolated in quantitative yield. GPC methods revealed the homopolymer topossess an M_(n) of 340,000 and an M_(w) of 1,650,000.

EXAMPLE 27

To a 50 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 35 ml dichloroethane and 1.55 g of a 9.1weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in dichloroethane (that had been dried over molecularsieves and purged with nitrogen) followed by catalyst component “A” (seeExample 35) (0.013 mmol), BF₃.etherate (0.117 mmol) and triethylaluminum(0.130 mmol). After one hour ethanol was injected to the solution toterminate the reaction. The polymer was then precipitated with excessethanol and was washed with excess acetone, filtered and driedovernight, under vacuum at 80° C. The graft copolymer was isolated in95% yield. GPC methods revealed the graft copolymer to possess an M_(n)of 71,000 and an M_(w) of 183,000.

EXAMPLE 28

To a 50 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 7.5 g of a 3.0 weight % solution of Diene55® in cyclohexane (that had been dried over molecular sieves and purgedwith nitrogen) followed by nickel ethylhexanoate (0.026 mmol) andethylaluminum dichloride (0.27 mmol). After one hour ethanol wasinjected to the solution to terminate the reaction. The graft copolymerwas then precipitated with excess ethanol and was washed with excessacetone, filtered and dried overnight, under vacuum at 80° C. Thepolymer was isolated in 84% yield (4.2 g). GPC methods revealed thegraft copolymer to possess an M_(n) of 121,000 and an M_(w) of 529,000.

EXAMPLE 29

To a 50 ml glass vial containing a magnetic stir bar and 2.5 g (26.5mmol) of norbornene was added 20 ml cyclohexane and 10.0 g of a 10.0weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in cyclohexane (that had been dried over molecularsieves and purged with nitrogen) followed by nickel ethylhexanoate(0.013 mmol) and methylaluminoxane (163 mmol). After one hour ethanolwas injected to the solution to terminate the reaction. The polymer wasthen precipitated with excess ethanol and was washed with excessacetone, filtered and dried overnight, under vacuum at 80° C. to affordthe product (1.5 g). GPC methods revealed the graft copolymer to possessan M_(n) of 13,400 and an M_(w) of 24,700.

EXAMPLE 30

To a 50 ml glass vial containing a magnetic stir bar and 2.5 g (26.5mmol) of norbornene was added 20 ml dichloroethane and 11.0 g of a 9.1weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in dichloroethane (that had been dried over molecularsieves and purged with nitrogen) followed by nickel ethylhexanoate(0.013 mmol), N,N-dimethyl anilinium tetra(perfluorophenyl)borate (0.013mmol) and triethylaluminum (650 mmol). After one hour ethanol wasinjected to the solution to terminate the reaction. The polymer was thenprecipitated with excess ethanol and was washed with excess acetone,filtered and dried overnight, under vacuum at 80° C. to afford theproduct (2.6 g). GPC methods revealed the graft copolymer to possess anM_(n) of 27,000 and an M_(w) of 44,000.

EXAMPLE 31

To a 50 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 20 ml dichloroethane and 11.0 g of a 9.1weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in dichloroethane that had been dried over molecularsieves and purged with nitrogen) followed by nickel ethylhexanoate(0.013 mmol), N,N-dimethyl anilinium tetra(perfluorophenyl)borate (0.013mmol) and triethylaluminum (650 mmol). After one hour ethanol wasinjected to the solution to terminate the reaction. The polymer was thenprecipitated with excess ethanol and was washed with excess acetone,filtered and dried overnight, under vacuum at 80° C. to afford the graftcopolymer (4.1 g) which was found by GPC methods to possess an M_(n) of39,000 and an M_(w) of 65,000.

EXAMPLE 32

To a 50 ml glass vial containing a magnetic stir bar and 5.0 g (53.1mmol) of norbornene was added 20 ml cyclohexane and 10.0 g of a 10.0weight % solution of polybutadiene with an M_(n) of 5,000 and a vinylcontent of 20%, in cyclohexane (that had been dried over molecularsieves and purged with nitrogen) followed by nickel ethylhexanoate(0.013 mmol), N,N-dimethyl anilinium tetra(perfluorophenyl)borate (0.013mmol) and triethylaluminum (650 mmol). After one hour ethanol wasinjected to the solution to terminate the reaction. The polymer was thenprecipitated with excess ethanol and was washed with excess acetone,filtered and dried overnight, under vacuum at 80° C. The polymer wasisolated in 32% yield and was found by GPC methods to possess an M_(n)of 38,000 and an M_(w) of 77,000.

These examples demonstrate the synthesis of ABA block copolymer5sconsisting of polynorbornene A blocks and polydimethsiloxane B block byutilizing the ivnyl groups present at the end of each norbornene chain,and an α,ω-dihydride terminated polydimethylsiloxane in a hydrosilationreaction.

EXAMPLE 33 Preparation of a Vinyl-terminated Poly(norbornene)

To a 500 ml stainless steel reactor that had been heated to 70° C. undera full vacuum for 18 hours then cooled, was added 100 g (1.06 mol)norbornene in dichloroethane (400 ml). The reactor was pressurized withethylene to a pressure of 150 psig. Thereafter catalyst component “A”(see Example 35) (0.435 g, 0.266 mmol) in 2 ml dichloroethane wasinjected followed by 0.31 ml (2.39 mmol) BF₃.etherate and 1.59 ml (2.66mmol) 1.7M triethylaluminum. After 60 minutes, 10 ml ethanol wasinjected to short stop the reaction and the resulting polymer was washedwith an excess methanol, filtered, and dried overnight, under vacuum at80° C. The resulting polymer (83.0 g) was found by GPC methods topossess an M_(n) of 2,350 and an M_(w) of 5,050 and was terminated witha vinyl group as witnessed by the proton and ¹³C NMR spectra.

Preparation of a Polynorbornene-poly(dimethylsiloxane)-poly(norbornene)Block Copolymer

To a 100 ml three neck round bottom flask equipped with a stirring bar,condenser and gas inlet adaptor was added (in a dry box) 5.0 g of avinyl terminated polynorbornene of M_(n) 2,350.

To a 30 ml glass vial was added 1.69 g -dihydride terminatedpolydimethylsiloxane with a molecular weight (M_(n)) of 400. The bottlewas purged with N₂ and filled with toluene to dissolve the polymer,which was then added to the round bottom flask with the polynorbornene.The mixture was heated to 40° C. and allowed to completely dissolve. Tothis solution was added 0.01 ml of catalyst component “B” (see Example35), and the flask was heated to 60° C. for 19 hours. The polymer wasprecipitated and washed with an excess methanol, filtered and driedovernight, under vacuum at 80° C. The block copolymer was isolated inquantitative yield and was found by GPC methods to possess an M_(n) of5,400 and an M_(w) of 7,700.

EXAMPLE 34 Preparation of aPolynorbornene-poly(dimethylsiloxane)-poly(norbornene) Block Copolymer

To a 100 ml three neck round bottom flask equipped with a stirring bar,condensor and gas inlet adaptor was added (in an inert gas filled drybox) 2.5 g of a vinyl terminated polynorbornene of M_(n) 2350 and 25 mltoluene.

To a 50 ml glass vial was added 15.0 g α,ω-dihydride terminatedpoly(dimethylsiloxane) of molecular weight (M_(n)) 17,500. The bottlewas purged with N₂ and filled with 50 ml toluene to dissolve thepolymer, which was then added to the round bottom flask with thepolynorbornene/toluene solution. The mixture was heated to 50° C. andallowed to completely dissolve. To this solution was added platinumdivinyl complex (0.1 ml in xylene, purchased from United ChemicalTechnologies) and the flask was heated to 90° C. for 72 hours. Thepolymer was precipitated and washed with an excess methanol, filteredand dried overnight, under vacuum at 80° C. The block copolymer wasisolated in quantitative yield. Proton NMR methods indicated that thehydride terminated poly(dimethylsiloxane) had reacted to completion andthe vinyl terminated poly(norbornene) was also essentially fullyconverted.

EXAMPLE 35 Preparation of a Vinyl-terminated Poly(norbornene)

To a 500 ml stainless steel reactor that had been heated to 70° C. undera full vacuum for 18 hours then cooled, was added 100 g (1.06 mol)norbornene in dichloroethane (400 ml). The reactor was pressurized withethylene (6 psig). Thereafter catalyst component “A” (0.435 g, 0.266mmol) in 2 ml dichloroethane was injected followed by BF₃.etherate (0.31ml, 2.39 mmol) and 1.7M triethylaluminum (1.59 ml, 2.66 mmol). After 60minutes, 10 ml ethanol was injected to short stop the catalyst and theresulting polymer was washed with an excess methanol, filtered and driedovernight, under vacuum at 80° C. The polymer was isolated in 94% yieldand was found by GPC methods to possess an M_(n) of 17,700 and an M_(w)of 68,600 and was terminated with a vinyl group as witnessed by theproton and ¹³C NMR spectra.

Preparation of a Polynorbornene-poly(dimethylsiloxane)-poly(norbornene)Block Copolymer

To a 100 ml three neck round bottom flask equipped with a stirring bar,condenser and gas inlet adaptor was added (in a dry box) 5.0 g of theabove-described vinyl terminated polynorbornene of M_(n) 17,700dissolved in 300 ml p-xylene.

To a 100 ml glass vial was added 17.1 g α,ω-dihydride terminatedpoly(dimethylsiloxane) of M_(n1452) 62,000. The bottle was purged withN₂ and filled with 100 ml p-xylene to dissolve the polymer, which wasthen added to the round bottom flask containing the polynorbornenesolution. The mixture was heated to 60° C. To this solution was addedplatinum divinyl complex (0.1 ml in xylene, purchased from UnitedChemical Technologies) and the flask was heated to 60° C. for 19 hours.The polymer was precipitated and washed with an excess methanol,filtered and dried overnight, under vacuum at 80° C. The block copolymerwas isolated in quantitative yield.

Catalyst Component “A”

Hexafluoroantimonic acid (HSbF₆, 0.45 g, 1.90 mmole) was placed in adry, nitrogen filled Teflon® bottle with a Teflon® cap/valve containinga magnetic stir-bar and the contents were cooled to −27° C. Thereafterwas added nickel ethylhexanoate (8% in mineral spirits, 1.90 mmole) andthe resulting mixture was allowed to warm to ambient temperature and wasthen stirred at ambient temperature for 2 hours.

Catalyst Component “B”

To a clean, dry 100 ml 2-necked flask equipped with a magnetic stir-barwas added H₂PtCl₆.6H20 (1.0 g, 2.45 mmol), ethanol (6.4 ml, 108 mmol),1,3-divinyl-tetramethyldisiloxane (2.4 ml, 10.73 mmol) and sodiumbicarbonate (2.0 g, 23.8 mmol). The mixture was refluxed for 45 minutesand thereafter the heat was removed and the brown mixture was allowed tostand at ambient temperature for 16 hours. The mixture was then filteredunder nitrogen and the ethanol removed under vacuum to afford a brownoil. The oil was redissolved in toluene, filtered again and the tolueneremoved under vacuum to afford the catalyst as a brown oil.

EXAMPLE 36

This example illustrates the copolymerization of ethylene and a vinylterminated PNB to give a comb block copolymer of PNB attached to abackbone of polyethylene.

Formation of Comb Block Copolymer

2.0 g vinyl terminated polynorbornene with a molecular weight (M_(n)) of1250 was dissolved in 300 ml of dried, degassed toluene. This mixturewas added to a 0.5 liter reactor and heated to 80° C. with agitation. Atoluene solution of 5.0 mg of (dimethylsilyl) bis (indenyl) zirconiumdichloride was added to the mixture followed by a toluene solution of5.5 g 10% methylaluminoxane. The reaction was allowed to continue for0.5 hour under continous ethylene feed at 60 psig. The reaction wasterminated by releasing the ethylene pressure and injecting 10 ml ofmethanol. The polymer was isolated by filtering through a Buchnerfunnel. This material was stirred with 10% acidic methanol thenrefiltered and washed with methanol followed by water. The polymer wasvacuum dried overnight at 80° C. (Yield 18.93 g). The formation of thiscomb block copolymer was confirmed by ¹H NMR spectroscopy after theproduct was washed with hot chloroform to eliminate any unreacted vinylterminated polynorbornene. The comb block copolymer exhibited resonancesat 1.4 ppm (indicating the presence of polyethylene runs) and 0.8-2.5ppm (indicating the incorporation of the norbornene macromonomer) butwas devoid of resonances at 5.0 and 5.8 ppm (indicating the abscence ofunreacted vinyl terminated polynorbornene.)

EXAMPLE 37

This example demonstrates the use of PMMA/PNB graft copolymer ascompatibilizer between PMMA and PNB homopolymers:

Optical microscopy was used to evaluate the PMMA-PNB graft copolymersability to act as a phase compatibilizer for blends of medium molecularweight PMMA and high molecular weight PNB homopolymers. Polymersolutions were prepared in chlorobenzene at room temperature. Polymerfilms were then solution cast onto glass microscope slides.Chlorobenzene was removed, by heating the sample in a vaccum oven at120° C. for 12 hours followed by further heating to 160° C. for 2 hours.Samples were then placed on the microscopy stage for analysis. Themagnification on the microscope was 100 times. Two blend samples wereprepared. Sample 1 is 90/10 weight % mixture of polynorbornene and PMMAhomopolymers that were blended in solution. Two distinct phases, roundedwhite PMMA phase dispersed in a dark polynorbornene matrix, are clearlyvisible. The white PMMA phase was observed to be present throughout thesample, with a broad distribution of sizes with a mean of 4.9 μm and astandard deviation of 4.1 μm. Sample 2 is a blend of sample 1 to which10 weight % of PNB-g-PMMA had been added in solution. The graftcopolymer behaving as a polymeric emulsifier increasing the interfacialinteraction between the PNB and the PMMA to reduce the domain size. Themost noticeable change in the micrograph is the uniformity of the PMMAdomains. The size distribution of the PMMA phase was observed to besomewhat narrower, with a mean of 3.7 μm, standard deviation of 1.6 μm.This sample was also observed to wet the glass slide much better thanthe uncompatibilized sample.

EXAMPLE 38

Polynorbornene homopolymer was reacted with maleic anhydride (MA) toform grafts of succinic anhydride at various percentages (from 0.3 to4.2%) in chlorobenzene or o-dichlorobenzene with benzoyl peroxide ordi-t-butyl peroxide as initiators under nitrogen purge. A typicalreaction used 16.8 g pnb homopolymer 12.5 g of maleic anhydride, 1.6% ofbenzoyl peroxide (0.2 g) in 200 ml di-chlorobenzene under nitrogen. Theresults in the table below show that the conditions for graftingpolynorbornene are favored at 140° C. with benzoyl peroxide as theinitiator. In the di-t-butyl peroxide system (experiment 4) a gel wasformed at room temperature following the reaction. This result indicatedthat coupling occurred during the reaction at 160° C. In order to avoidthe coupling reaction, the reaction temperature was decreased to 140° C.and the reaction time was extended to 24 hours to lower the free radicalconcentration in the reacting system. This polymer had 4.2% (by wt.)grafting and was slightly yellowish. The percentage of grafting wasmeasured by modification of a literature method (J. Polym. Polym. Lett.Ed. 21, 2, 1993).

Benzoyl Experi- Rxn Rxn peroxide Di-t-butyl MA ment Time Temp (% ofperoxide Graft No. (hr) (° C.) MA) (ml) (wt %) Comments 1 2 120 2 — 0.3white product 2 3 130 4 — 0.6 white product 3 5 140 3.5 — 1.1 whiteproduct 4 2 160 — 1 4 yellow, gel formation at low conc. (5%) 5 24 140 —1 4.2 slightly yellowish, no gel formation

EXAMPLE 39

Copolymers of decylnorbornene and norbornene were reacted with maleicanhydride (MA) to form grafts of succinic anhydride in chlorobenzene oro-dichlorobenzene with benzoyl peroxide or di-t-butyl peroxide asinitiators under nitrogen atmosphere. When di-t-butyl peroxide was usedas an initiator at various temperatures (experiments 4 and 5 in thetable below) the viscosities of polymer solutions were low following thereaction and the particle sizes of the polymers after precipitation weresmall and hard to filter. These results indicate that some degradationof the polymer may have occured during the reaction. Therefore,di-t-butyl peroxide was not favored as an initiator for grafting ofdecylnorbornene copolymers. The results (experiments 1, 2, 3, 6, and 7)obtained with benzoyl peroxide as an initiator show that a white powdercould be obtained indicating slight, if any, degradation. Thepolynorbornene could be grafted with various amounts of the maleicanhydride. It seems that, unlike homo-polynorbornene systems, benzoylperoxide is more suitable than di-t-butyl peroxide as an initiator incopolymers containing decylnorbornene.

Experi- Rxn Rxn Benzoyl Di-t-butyl ment Tg pnb Time Temp peroxideperoxide MA Graft Comments No. (° C.) (hr) (° C.) (% of MA) (ml) (wt %)(Mw = 200,000) 1 232 3 140 1.6 — 1.1 white product Mw = 148,000 2 232 1160 4.7 — 2.0 white product Mw = 98,000 3 232 1.5 160 6.4 — 3.7 whiteproduct 4 232 2 140 — 1 >6.0 white product 5 232 1.5 160 — 0.2 ? whiteproduct 150 3 140 0.8 — 0.5 white product 7 150 3 140 1.6 — 1.1 whiteproduct

EXAMPLE 40

The PNB homo- and copolymers and nylon have different solubilityparameters. To make possible the reactive solution blending of graftedPNBs with nylon, a solvent pair was used to dissolve both polymers. Thereactive blending of grafted polynorbornenes with nylon was performedusing a phenol/o-dichlorobenzene solution (30/130, w/w) at 130° C. Sincethe phenol was also as a nucleophile, nylon was dissolved in reactionmixture first, followed by addition of grafted polynorbornenes to avoidesterification.

Experi- ment No. pnb (% g) nylon Properties of Polymers 1 homo- (4.2%)6,6 clear film, insoluble in 50% (Ex. 38-5) (crystalline) formic acid,increased 50% toughness 2 s.c. (1.l%) 6,6 clear film, partially solublein 50% (Ex. 39-1) (crystalline) formic acid, increased 50% toughness 3s.c. (2.0%) 12 (crystalline) clear film, Tm: 180° C., T_(g): 67% (Ex.39-2) 33% 232° C., increased toughness 4 s.c. (2.0%) (amorphous) clearfilm, Tg: 160° C., T_(g): 66% (Ex. 39-2) 33% 232° C., increasedtoughness 5 s.c. (3.7%) 6,6 Tm: 260° C. 50% (Ex. 39-3) (crystalline) 50%6 s.c. (3.7%) 12 (crystalline) Tm: 180° C. 50% (Ex. 39-3) 50%

Experiment 5,6 clearly shows IR evidence of the reaction of the amineterminated nylons for the phthalamide structure (dicarboximide) by apeak at 1710 cm⁻¹.

Experiment 5 exhibits mechanical and thermal properties intermediatebetween the constituents indicating a successful polymer alloy.Non-reactive blends exhibited mechanical properties inferior to theconstituents. For example, the strain to break was observed to be 0.7%for the NB-type polymer, 7.7% for the Nylon 6,6 and 1.7% for the alloy.

Experiment 6 exhibits the novel characteristic of having mechanical andthermal properties superior to the individual constituents indicating asynergistic alloy. For example, the NB polymer was observed to have astrain to break of 0.7%, 3.6% for the Nylon 2, and 6.1% for the alloy.

EXAMPLE 41

This example demonstrates the coupling of commercially availabletoughners to the PNB/succinic anhydride graft copolymers of thisinvention. Amine terminated polypropylene oxide (Jeffamine®) and amineterminated polybutadienes (Hycar® ATBN) were grafted onto PNB/succinicanhydride copolymers.

Amine Terminated Polybutadiene Ex- peri- ment Hycar ® Reaction No. PNB(% g) ATBN Conditions Properties 1 s.c. (3.7% MA) ATBN 120° C. gelformation (Tg = 232° C.) 1300X21 dichlorobenzene after 2 min., 90% 10%high cross- (Ex 39, 3) linking in reaction 2 s.c (1.1% MA) ATBN Roomwhite product, (Tg = 232° C.) 1300X21 Temperature low clarity of 90% 10%dichlorobenzene film, color (Ex. 39-1) change after press at 305° C.,tougher 3 s.c. (1.1% MA) ATBN Room white product, (Tg = 232° C.) 1300X21Temperature low clarity of 95% 5% dichlorobenzene film, color (Ex. 39-1)change after press at 305° C., tougher 4 s.c. (0.5% MA) ATBN Room whiteproduct, (Tg = 150° C.) 1300X45 Temperature excellent 95% 5%chlorobenzene, clarity of film, (Ex. 39-6) colorless, very tough, DMA,Flexural module test 5 s.c. (0.5% MA) ATBN Room white product, (Tg =150° C.) 1300X45 Temperature excellent 90%, 10% chlorobenzene clarity offilm, (Ex. 39-6) very tough, colorless

To avoid the thermo-oxidation of the ATBN during the process, two typesof polynorbornenes (T_(g): 232° C. & 150° C.) were chosen for theseruns. When a polynorbornene with a high maleic anhydride content wasused, a gel formed upon addition of the ATBN after reacting for 2 min.This result indicated that crosslinking occurred during the reaction andthat the reactivity of the amine group on Hycar® was high at 120° C.Subsequent studies used lower grafting contents and lower reactiontemperatures. While the reaction products using room temperature andlower grafted amounts of maleic anhydride looked good, the products werenot stable at 305° C. which was required for pressing the films (colorchange and films of low clarity). These results indicate that theimpurity (alkyl amine) and the unsaturation of the ATBN might affect thecolor intensity and clarity of the film. Therefore, a high purity ATBNHYCAR® (ATBN 1300×45) and low glass transition temperaturepolynorbornene (Tg=150° C.) were used to investigate Hycar® toughening.The sample with the best visual appearance (experiment 4) yielded filmshaving excellent clarity, very low color intensity and very goodtoughness.

Reactive Blending: Grafted Polynorbornene & Jeffamine ® Experi- mentJeff- No. pnb(%-g) amine ® Properties of Polymers 6 homo-(4.2%-g) D-2000difficulty to filter, swell or gel 70%(Ex. 38-5) 30% no furtherinvestigation 7 s.c. (1.0%) D-2000 white product, excellent clarity90%(Ex. 39-1) 10% of film, colorless, color change after pressing at305° C., tough, T_(g) = 194° C. 8 s.c.(1.0%) ED-2001 whiteproduct-strain at break = 90%(Ex 39-1) 10% 3.3%

In the homo-polynorbornene system, the product was very difficult toisolate and no further investigation was performed. The amine terminedpolypropylene oxide (ATPO) (experiment 7) was reacted with side chainplasticized polynorbornene (norbornene/decylnorbornene copolymer) atroom temperature. A colorless and highly transparent film was cast fromthe reaction mixture. The film had very good toughness. However, thecolor changed after pressing the film at 305° C. To allow better hightemperature performance, an ATPO having a higher degree of amination wasemployed (experiment 8). The product was colorless after drying at 150°C. for 4 hours under vacuum. Infrared analysis showed evidence for thephthalimide structure, but with other groups contributing to the 1735cm⁻¹ band, changing the usual ratio of the 1710 cm⁻¹ to the 1735 cm⁻¹band which is characteristic of the phthalimide structure.

EXAMPLE 42

Experi- ment No. pnb(%-g) Silicone Properties of Polymers 1 s.c.(1.0%)DMS-A21 colorless, transparent film from 90% 10% solution casting,toughness increased (Ex. 39-1) after exposure to 150° C. for 3 hours 2s.c.(1.0%) DMS-A32 colorless, transparent film from 90% 10% solutioncasting, toughness increased (Ex. 39-1) after exposure to 150° C. for 3hours 3 s.c.(1.0%) DMS-A15 colorless, transparent film from 90% 10%solution casting, toughness increased (Ex. 39-1) after exposure to 150°C. for 3 hours 4 s.c.(1.0%) DMS-A21 Excellent clarity of film and bar90% 10% were obtained after pressing at (Ex. 39-1) 305° C.-strain abreak = 3.3%

Amine terminated silicones were coreacted with maleic anhydride graftedpolynorbornene. In this investigation, various molecular weights ofamine terminated silicones were chosen to toughen the polynorbornene.The results of reactions of silicones with grafted polynorbornenes atroom temperature with the composition fixed at 10% amine terminatedsilicone are set forth below. The reactions were allowed to proceedovernight. Films that were cast from the reaction solution were brittle,but highly transparent. However, the films increased in toughness afterheating in the vacuum oven at 130° C. The reaction products which hadbeen dried similarly in the vacuum oven could not be pressed into films,presumably because the drying at elevated temperatures caused somecrosslinking. An alternative method (experiment 4) was carried out bydrying the sample at room temperature under vacuum, then transparent,colorless films and DMA bars could be obtained by pressing the uncuredsample at 305° C.

Mechanical testing was performed on thin films in tension. The strain atbreak for the silicone film was 3.3%, which is again better than 0.6%for the base copolymer. Flexural modulus exhibited a strain to break of3.1%, with a Flexural modulus of 177,000 psi, not much below the 181,000psi for the base copolymer. Infrared analysis showed evidence for thephthalimide structure.

EXAMPLE 43

This example demonstrates that high T_(g) (380°) polycyclic additionpolymers (polynorbornene M_(w)=200,000) can be plasticized byhydrocarbon plasticizers.

A hydrogenated cyclopentadiene (CPD) oligomer (T_(g) 85° C., M_(w) 480,available under the Escorez trademark, Exxon Chemicals) was blended withpolynorbornene homopolymer. One gram mixtures of the PNB/CPD oligomerwere dissolved in 25 ml chlorobenzene and precipitated in 1000 ml ofchilled methanol. Blended samples gave transparent film. The movement ofthe T_(g) and the transparency of the films suggest that these materialsare miscible. Results are set forth below:

Experiment No. wt % Fraction PNB Blend T_(g (° C.)) 1 0.50 178 2 0.60187 3 0.70 207 4 0.80 239 5 0.90 294

T_(g) of the precipitated Escorez is around 93° C. Samples givetransparent films. The movement of the T_(g) and transparency suggestthat these materials are miscible.

Plasticization of PNB (norbornene/decylnorbornene copolymer, 10 mol %decylnorbornene, M_(w) 200,000) by linear alkanes is dependent on themolecular weight of the alkane, and requires decylnorbornene in the basecopolymer structure. With 20 volume % of the alkane, the followingresults were observed:

Experiment # Carbons in Tg Strain at Film No. Alkane (° C.) breakCharacteristics 6 — 282 <1% transparent 7 20 190 <1% transparent 8 22172 <1% transparent 9 24 138 1% transparent 10 28 120 3% transparent 1132 122 6% transparent 12 36 140 cloudy

Limited plasticization with homo-polynorbornene, can depress the T_(g)from 380° C. to 230° C. with C₃₀₊ alpha olefin, and to 260° C. withparaffin using the method described above.

KRATON® G/PNB blend: polynorbornene homopolymer (M_(n) 209,000) withKRATON® G (1652), more detailed study showed solution blend of 50%KRATON® G and 50% PNB and decylnorbornene copolymer gave the unusualresult of a transparent film, with domain sizes less than 1 μm, belowthe limit of detection with an optical microscope. Closer examination ofa cryogenically microtomed sample with TEM using RuO₄ stain indicated afine structure of approximately 15 nm. Tensile properties wereindicative of a co-continuous network with a Tensile modulus of 2 Gpaand a strain at break of 7% for the homopolynorbornene blend. Thiscompares to a tensile modulus of 70 MPa and a strain at break of 80% fora PNB of molecular weight of 2,000,000 which also gave domain sizes onthe order of 1 μm clearly indicating that KRATON® G is the continuousphase with PNB being the dispersed phase, also supported by microscopy.The high tensile modulus and low strain to break given the samecomposition (50 wt % PNB homopolymer/50 wt % KRATON® G) for exhibitingthe small domain size suggest that both constituents are contributing tothe mechanical properties and suggest a novel, co-continuous morphology.

EXAMPLE 44

Into a 100 ml single neck round bottom flask containing a magneticstirrer, was added 5.0 g (2.08 mmoles) of epoxy terminatedpolynorbornene of molecular weight (M_(n)) 2200 g/mole. To this 175 mlof tetrahydrofuran (THF) was added and after the polymer had dissolved,2 ml (6.25 mmoles) of 60 wt % perchloric acid in water was added,followed by 1 ml of de ionized water. The solution was stirred for 12hours at room temperature after which the polymer was isolated by slowlyadding the reaction solution into water. The precipitated polymer wasfiltered, dissolved in THF and was reprecipitated to remove any trace ofacid. The polymer was filtered, dissolved in chloroform and stirred overanhydrous magnesium sulfate to remove trace amounts of water, filteredover celite and solvent was removed using a rotovap to obtain a whitesolid. The solid was further dried at 50° C. in a vacuum oven. Yield4.45 g. The reaction was confirmed using ¹H NMR. The disappearance ofthe resonance's at 2.7 and 2.9 ppm and the appearance of new resonance'sat around 3.3 and 3.5 ppm corresponding to the methylene and the methineprotons attached to a hydroxyl group confirms the formation of the diol.

EXAMPLE 45

This example illustrates a reaction between monoalcohol and an acidchloride to give terminal ester functionality.

Into a 50 ml two neck round bottom fitted with a condenser and amagnetic stirrer, was added 3.0 g (0.75 mmoles) of monohydroxyterminated polynorbornene of molecular weight 4000 (M_(n)) g/mole. Tothis 100 ml of tetrahydrofuran (THF) and 0.6 ml (7.5 mmoles) of pyridinewas added. The polymer was allowed to dissolve after which 0.34 g (3.75mmoles) of acryloyl chloride was added, dropwise into the reactionflask. The solution was stirred for 10 hours at room temperature afterwhich the polymer was isolated by slowly adding the reaction solutioninto water. The precipitated polymer was filtered, and was transferredinto a separator funnel. The solution was washed several times withwater, followed by aqueous sodium bicarbonate solution. The chloroformlayer was separated from the aqueous layer, stirred over anhydrousmagnesium sulfate and carbon black, filtered over celite and solvent wasremoved using a rotovap to obtain a light tan color solid. The solid wasfurther dried at in a vacuum oven. Yield 1.85 g. The reaction wasconfirmed using ¹H NMR. The disappearance of the resonance 3.7 ppm andthe appearance of new resonance's at around 4.2 ppm corresponding to themethylene group attached to an ester group and the terminal alkeneprotons appearing at 5.8, 6.1 and 6.3 ppm's confirms the conversion ofthe hydroxy groups to the acrylic ester functionality.

EXAMPLE 46

This example demonstrates the grafting of acrylate type monomers on toPNB.

Into a two necked, 100 ml round bottom flask fitted with a overheadmechanical stirrer and an argon inlet, was added 1.0 g (5×10⁻⁶ moles) ofpolynorbornene (M_(w)≈200,000 g/mole) under argon atmosphere. To this,10 ml's of dichlorobenzene was syringed in and heated to 90° C. To this5.5 g (0.055 moles) of freshly distilled methyl methacrylate and 0.05 gof di t-butyl peroxide were added. The reaction was stirred for about 2hours at 90° C. during which time the solutions viscosity was observedto increase. After 2 hours, the flask was further heated to 150° C. forand held there for 3 hours. The solution was cooled, diluted withchloroform and precipitated into methanol to obtain a white polymer,which was dried at 100° C. in a vacuum oven. In order to thepolynorbornene/poly(methyl methacrylate) graft copolymer from thepoly(methyl methacrylate) homopolymer, a portion of the sample wasextracted with acetone and centrifuged to obtain an acetone solublefraction and an acetone insoluble fraction. ¹H NMR of the acetoneinsoluble fraction indicated the presence of pure poly(methylmethacrylate), while the ¹H NMR analysis of the acetone insolublepolymer indicated the presence of aliphatic ester protons at 3.6 ppmcorresponding to the poly(methyl methacrylate) and a broad peakappearing around 1-2.5 ppm corresponding to the aliphatic protons ofnorbornene polymer. Also films of the acetone insoluble material, castfrom cyclohexane was observed to be clear and transparent. The clearfilm obtained from the acetone insoluble material followed by thepresence of methyl ester protons from NMR are a clear evidence forgrafting of poly(methyl methacrylate) on to polynorbornene polymers. GPCperformed on the polymer indicated a single sharp peak with a weightaverage molecular weight of 485,000 and a polydispersity of 4.8.

EXAMPLE 47 Example for the Synthesis of Urethane/PNB Graft Copolymer

Into a 50 ml two neck round bottom fitted with a condenser and amagnetic stirrer, was added under an argon atmosphere, 0.45 g (0.187mmoles) of dihydroxy terminated polynorbornene of molecular weight 2400(M_(n)) g/mole. To this 10 ml of chlorobenzene and 0.01 ml of dibutyltindilaurate was added. The polymer was allowed to dissolve after which0.05 g (0.42 mmoles) of phenyl isocyanate was added, dropwise into thereaction flask. The solution was stirred for 5 hours at 125° C. afterwhich the polymer was isolated by slowly adding the reaction solutioninto methanol. The precipitated polymer was filtered, washed withmethanol and dried at 75° C. in a vacuum oven. Yield 0.39 g. Thereaction for the formation of the urethane linkage was confirmed using¹H NMR. The disappearance of the resonance 3.7 ppm corresponding to themethylene and the methine protons attached to an oxygen, followed by theappearance of new resonance at around 4.2 ppm corresponding to themethylene group attached to an ester, 6.4 corresponding to an amideproton and the aromatic protons appearing at 7.1 and 7.4 ppm's confirmsthe conversion of the hydroxy groups to the urethane functionality.

EXAMPLE 48

This example illustrates the ability to react amine-functional molecules(e.g., azo dyes) with a maleic anhydride-grafted PNB.

Grafting of aniline onto a maleic-anhydride grafted PNB.

A 1.1% maleic anhydride-grafted polynorbornene (5.0 g) was dissolved in100 mL toluene in a 3 neck 250 ml round bottom flask by heating thesample to 100° C. To this solution 48 microliters of aniline was added.The solution was allowed to react at 100° C. for an additional 45 min.About 50 ml of solvent were then removed by simple distillation. Thesolution was cooled to room temperature overnight. The mixture was thenpoured into MeOH (500 ml) to precipitate the polymer. Infrared analysisof the resulting material showed that both the amic acid and fullyimidized structure was present indicating that the aniline had reactedwith the maleic anhydride graft on the polynorbornene.

EXAMPLE 49

This experiment shows how incorporation of an appropriate comonomer intoPNB can change the miscibility of the PNB with a chosen polymer, in thiscase polystyrene.

a) Synthesis of 5-phenylnorbornene

Dicyclopentadiene (180 g), styrene (140 g), toluene (36 g), andN,N-diethylbydroxylamine (0.35 g) (added as a polymerization inhibitor)were added to a stainless steel reactor. The mixture was heated to 150°C. for 6 hours. The low boiling fraction was removed from the resultingreaction mixture on the roto-vap. The remaining higher boiling fractionwas fractionally distilled. The fraction distilling at 130° C. @ 4 mm Hgwas analyzed by GC and found to be 96% 5-phenylnorbornene.

b) Copolymerization of Norbornene and 5-phenylnorbornene

Norbornene (4.50 g) and 5-phenylnorbornene (0.90 g) were dissolved indichloroethane (60 ml). To this degassed solution was added[(crotyl)Ni(1,5-cyclooctadiene)]PF₆ (0.0095 g). Polymer began toprecipitate from solution after several minutes. After 1 hour themixture was added to MeOH to precipitate the remaining polymer. Afterfiltering and drying the solid, 1.92 g of powder was isolated. NMRanalysis determined the phenylnorbornene incorporation to be 35 mol %.By GPC determination, the M_(w)=333,000 and M_(n)=161,000.

c) Copolymerization of Norbornene and 5-phenylnorbornene

The procedure was the same as in the above example, except that thefollowing amounts of monomers were used: 5.0 g of 5-phenylnorbornene and2.45 g of norbornene. After the initial 0.0095 g of[(crotyl)Ni(1,5-cyclooctadiene)]PF₆ was added, no polymer precipitated,therefore an additional 0.095 g of [(crotyl)Ni(1,5-cyclooctadiene)]PF₆was added. After stirring overnight, the mixture was poured into 500 mlof MeOH to precipitate the polymer. After filtering and drying, 4.17 gof polymer was isolated. NMR analysis determined the phenylnorborneneincorporation to be 4 mol %. The M_(w) was determined to be 37,800 andthe M_(n) was determined to be 17,100 by GPC.

d) Miscibility of Norbornene/Phenylnorbornene Copolymers in Polystyrene

Norbornene/phenyl norbornene copolymers containing 4% and 35% phenylnorbornene. Blends of the above materials with polystyrene were preparedby dissolving the appropriate norbornene/phenyl norbornene copolymersand polystyrene in chloroform and precipitating the solution of the twopolymers in methanol. The precipitated polymers were filtered, dried ina vacuum oven at 120° C. for 12 hours, followed by further drying at180° C. for 2 hours. Using the above method, phenylnorbornene/norbornene copolymers were blended with polystyrene of twodifferent molecular weights; 5000 g/mole & 95,000 g/mole in a 75/25 wt.ratio. Miscibility of the two polymers was analyzed using differentialscanning calorimetric analysis (DSC). All DSC analysis were performedunder nitrogen atmosphere, at a heating rate of 20° C./min. DSC analysisof the norbornene/phenyl norbornene copolymers indicated a single T_(g),at 391° C. for the material containing 4% phenyl norbornene and at 299°C. for the material containing 35% phenyl norbornene. The glasstransition temperatures for polystyrene of molecular weights 5000 g/moleand 95,000 g/mole were observed to be 96° C. and 103° C. respectively.DSC analysis on the blends of norbornene/phenyl norbornene copolymercontaining 4% of phenyl norbornene and polystyrene of molecular weight5000 g/mole indicated two glass transitions at 95° C. and 382° C., thusindicative of a immiscible system. But the DSC analysis on the blends ofnorbornene/phenyl norbornene copolymer containing 35% of phenylnorbornene and polystyrene of molecular weight 5000 g/mole indicatedonly one glass transition in-between the two homo-polymer glasstransition temperatures at around 220° C. indicative of a misciblesystem. Changing the molecular weight of the polystyrene to 95,000g/mole from 5000 g/mole, results in the appearance of two glasstransition temperatures for both the 4% and 35% poly(norbornene/phenylnorbornene)/polystyrene blend samples corresponding to the glasstransition temperatures of the homopolymers. It should be pointed outthat the second glass transition temperature corresponding to thepoly(norbornene/phenyl norbornene) copolymer containing 35% phenylnorbornene comonomer was broad indicating probably partial miscibilitywith the high molecular weight polystyrene.

EXAMPLE 50

These experiments show that PNB can be chlorinated either by photolysis(if the polymers are saturated) or without photolysis (if the polymersare unsaturated).

Equipment

Chlorination reactions were carried out in a jacketed, cylindrical,ACE-glass reaction flask with a multiport head fitted with a stirrer,Dewar condenser, thermometer well, vacuum port and a gas dip tube.Ultraviolet initiation was obtained using blacklight flourescentcircleline lamps which surrounded the reactor. The chlorine feed systemconsisted of a continuosly weighed chlorine lecture bottle connected tothe gas dip tube. Chlorine flow was manually controlled with athrottling valve. A high purity nitrogen supply was also connected tothe gas dip tube. The reaction temperature was controlled with a Haakecirculating water bath.

Experimental Procedure

In a typical solution chlorination the reactor was charged with theresin and 1,1,2,2-tetrachloroethane and then brought to 50°-60° C. withstirring to effect dissolution. After dissolution the reaction systemwas evacuated and purged with nitrogen twice. The system was thenevacuated and chlorine was introduced until the solution was saturatedas indicated by chlorine condensing in the Dewar which was filled withdry ice. All reactions were run at near atmospheric pressure. The UVlights were activated upon achieving saturation (chlorinations of thevinyl terminated and 5-ethylidene-2-norbornene copolymers were conductedwithout UV light in an aluminum foil-shielded reactor). Chlorine wasadded continuously until the amount needed to reach the desired combinedchlorine level was achieved. Reaction times were less than one hour. Thegaseous hydrochloric acid that formed during the reaction passed throughthe Dewar uncondensed to a caustic scrubber. The reactor contents werepurged with nitrogen after reaction to remove excess chlorine to thecaustic scrubber. The chlorinated polymer was recovered from solution byslow addition to methanol with agitation. The precipitated polymer wasfiltered, washed with methanol, filtered and dried under vacuum at50°-60° C. for 24-48 hours. See the table below for details ofexperiments and analytical results.

Chlorination of Norbornene Homo- and Copolymers

Experi- Polymer ment Starting Cone Calorimetry No. Material* Photolysis% Cl Results 1 NB/NB-10 yes 25 — copolymer 2 NB yes 27 — homopolyer 3NB/ENB no 25 — copolyer 4 vinyl-term no 15 — PNB 5 NB-10 yes 23chlorinated poly- homopolyer mer-890 KW/m² control polymer- 1840 KW/m² 6NB/NB-10 yes 24 — copolymer *NB = norbornene NB-10 =5-decyl-2-norbornene vinyl-term = vinyl terminated

We claim:
 1. A polycyclic addition polymer consisting essentially ofpolycyclic repeating units wherein a portion of said repeating unitscontain pendant epoxide containing substituents represented by theformula:

wherein n is 0 to 4, and R¹ to R⁴ independently represents hydrogen,linear and branched C₁ to C₂₀ alkyl, hydrocarbyl substituted andunsubstituted C₅ to C₁₀ cycloalkyl, C₆ to C₂₄ aryl, and C₇ to C₁₅aralkyl, with the proviso that at least one of R¹ to R⁴ alone or takentogether represents an epoxide containing substituent.
 2. The polymer ofclaim 1 wherein at least one of R¹ to R⁴ is selected from an epoxidesubstituent represented by the group:


3. The polymer of claim 1 containing a repeating unit wherein R³ and R⁴are taken together with the ring carbon atom to which they are attachedto form a repeating unit represented by the structure:


4. The polymer of claim 1 containing a repeating unit wherein R¹ and R⁴taken together with the two ring carbon atoms to which they are attachedto form a repeating unit represented by the structure:


5. A polycyclic addition polymer consisting essentially of polycyclicrepeating units represented by the formula:

wherein n is 0 to 4, and R¹ to R⁴ independently represents hydrogen,linear and branched C₁ to C₂₀ alkyl, hydrocarbyl substituted andunsubstituted C₅ to C₁₀ cycloalkyl, C₆ to C₂₄ aryl, and C₇ to C₁₅aralkyl, and wherein one terminal end of the polymer chain is terminatedwith an epoxide group.
 6. The polymer of claim 5 wherein the terminalepoxide group is selected from a substituent represented by the group:


7. A polycyclic addition polymer consisting essentially of polycyclicrepeating units wherein a portion of said repeating units containpendant epoxide containing substituents and wherein one terminal end ofthe polymer chain is terminated with an epoxide group, said repeatingunit containing the pendant epoxide repeating substituent is representedby the structure:

wherein n is 0 to 4, and R¹ to R⁴ independently represents hydrogen,linear and branched C₁ to C₂₀ alkyl, hydrocarbyl substituted andunsubstituted C₅ to C₁₀ cycloalkyl C₆ to C₂₄ aryl, and C₇ to C₁₅aralkyl, with the proviso that at least one of R¹ to R⁴ alone or takentogether represents said pendant epoxide containing substituent.
 8. Thepolymer of claim 7 wherein at least one of R¹ to R⁴ is selected from anepoxide substituent represented by the group:


9. The polymer of claim 7 containing a repeating unit wherein R³ and R⁴are taken together with the ring carbon atom to which they are attachedto form a repeating unit represented by the structure:


10. The polymer of claim 7 containing a repeating unit wherein R¹ and R⁴taken together with the two ring carbon atoms to which they are attachedto form a repeating unit represented by the structure:


11. The polymer of claim 7 wherein the terminal epoxide group isselected from a substituent represented by the group: